JP2012214745A - Catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing polyolefin using the same - Google Patents
Catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing polyolefin using the same Download PDFInfo
- Publication number
- JP2012214745A JP2012214745A JP2012070510A JP2012070510A JP2012214745A JP 2012214745 A JP2012214745 A JP 2012214745A JP 2012070510 A JP2012070510 A JP 2012070510A JP 2012070510 A JP2012070510 A JP 2012070510A JP 2012214745 A JP2012214745 A JP 2012214745A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- ion
- layered silicate
- component
- olefin polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 177
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 81
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 64
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 110
- 238000005342 ion exchange Methods 0.000 claims abstract description 101
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 75
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 51
- 238000001179 sorption measurement Methods 0.000 claims abstract description 51
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 121
- 238000010306 acid treatment Methods 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000002685 polymerization catalyst Substances 0.000 claims description 21
- 150000002500 ions Chemical class 0.000 claims description 11
- 230000000737 periodic effect Effects 0.000 claims description 9
- 229910021647 smectite Inorganic materials 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 48
- 230000000694 effects Effects 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- 150000004760 silicates Chemical class 0.000 abstract description 10
- 230000000704 physical effect Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 85
- 238000011282 treatment Methods 0.000 description 81
- -1 silicate compound Chemical class 0.000 description 68
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 64
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 63
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 62
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 60
- 229910052901 montmorillonite Inorganic materials 0.000 description 60
- 239000000126 substance Substances 0.000 description 54
- 239000004743 Polypropylene Substances 0.000 description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 44
- 238000010828 elution Methods 0.000 description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 39
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 36
- 239000005977 Ethylene Substances 0.000 description 36
- 239000000203 mixture Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 30
- 239000002002 slurry Substances 0.000 description 28
- 238000005469 granulation Methods 0.000 description 27
- 230000003179 granulation Effects 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 26
- 239000004927 clay Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 229920001155 polypropylene Polymers 0.000 description 24
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- 239000010410 layer Substances 0.000 description 21
- 125000004429 atom Chemical group 0.000 description 20
- 150000002430 hydrocarbons Chemical group 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 230000035484 reaction time Effects 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 239000003446 ligand Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 125000001424 substituent group Chemical group 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 125000004434 sulfur atom Chemical group 0.000 description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 239000001257 hydrogen Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 5
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003828 azulenyl group Chemical group 0.000 description 4
- 239000002734 clay mineral Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012066 reaction slurry Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OUEIHUFHNUEPQU-UHFFFAOYSA-L CC1=CC(C)=C(C=2OC=CC=2)C1[Zr](Cl)(Cl)(=[Si](C)C)C1C(C)=CC(C)=C1C1=CC=CO1 Chemical compound CC1=CC(C)=C(C=2OC=CC=2)C1[Zr](Cl)(Cl)(=[Si](C)C)C1C(C)=CC(C)=C1C1=CC=CO1 OUEIHUFHNUEPQU-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000012993 chemical processing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- LOKCKYUBKHNUCV-UHFFFAOYSA-L dichlorozirconium;methylcyclopentane Chemical compound Cl[Zr]Cl.C[C]1[CH][CH][CH][CH]1.C[C]1[CH][CH][CH][CH]1 LOKCKYUBKHNUCV-UHFFFAOYSA-L 0.000 description 2
- RKGLUDFWIKNKMX-UHFFFAOYSA-L dilithium;sulfate;hydrate Chemical compound [Li+].[Li+].O.[O-]S([O-])(=O)=O RKGLUDFWIKNKMX-UHFFFAOYSA-L 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- GRMXFZGBPICEAU-UHFFFAOYSA-N 2-methylocta-1,7-diene Chemical compound CC(=C)CCCCC=C GRMXFZGBPICEAU-UHFFFAOYSA-N 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- RSPAIISXQHXRKX-UHFFFAOYSA-L 5-butylcyclopenta-1,3-diene;zirconium(4+);dichloride Chemical compound Cl[Zr+2]Cl.CCCCC1=CC=C[CH-]1.CCCCC1=CC=C[CH-]1 RSPAIISXQHXRKX-UHFFFAOYSA-L 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- SFCBEITXAISJJQ-UHFFFAOYSA-N C(C)(C)C=1C=C(C=2CC3=CC=C(C=C3C=2C=1)C(C)C)[Ti] Chemical compound C(C)(C)C=1C=C(C=2CC3=CC=C(C=C3C=2C=1)C(C)C)[Ti] SFCBEITXAISJJQ-UHFFFAOYSA-N 0.000 description 1
- XZEPPKSYNAACOP-UHFFFAOYSA-N C1(=CC=CC=2C3=CC=CC=C3CC12)[Ti] Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC12)[Ti] XZEPPKSYNAACOP-UHFFFAOYSA-N 0.000 description 1
- CAWVBEDTWLNFKY-UHFFFAOYSA-N C1=CC=C2C([Ti])C(C)=CC2=C1 Chemical compound C1=CC=C2C([Ti])C(C)=CC2=C1 CAWVBEDTWLNFKY-UHFFFAOYSA-N 0.000 description 1
- AZJUENLYODNSDZ-UHFFFAOYSA-L C=1C=COC=1C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)(=[Si](C)C)C(C1=CC=CC=C1C=1)C=1C1=CC=CO1 Chemical compound C=1C=COC=1C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)(=[Si](C)C)C(C1=CC=CC=C1C=1)C=1C1=CC=CO1 AZJUENLYODNSDZ-UHFFFAOYSA-L 0.000 description 1
- UICVFNLOYAPXPE-UHFFFAOYSA-L C=1C=CSC=1C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)(=[Si](C)C)C(C1=CC=CC=C1C=1)C=1C1=CC=CS1 Chemical compound C=1C=CSC=1C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)(=[Si](C)C)C(C1=CC=CC=C1C=1)C=1C1=CC=CS1 UICVFNLOYAPXPE-UHFFFAOYSA-L 0.000 description 1
- JVSQYFQOFKFOQM-UHFFFAOYSA-L CC1=CC(=C(C)C1[Zr](Cl)(Cl)(C1C(C)=CC(=C1C)C1=CC=CC=C1)=[Si](C)C)C1=CC=CC=C1 Chemical compound CC1=CC(=C(C)C1[Zr](Cl)(Cl)(C1C(C)=CC(=C1C)C1=CC=CC=C1)=[Si](C)C)C1=CC=CC=C1 JVSQYFQOFKFOQM-UHFFFAOYSA-L 0.000 description 1
- OXLXAPYJCPFBFT-UHFFFAOYSA-L CC1=CC(C)(C=C1)[Zr](Cl)(Cl)C1(C)C=CC(C)=C1 Chemical compound CC1=CC(C)(C=C1)[Zr](Cl)(Cl)C1(C)C=CC(C)=C1 OXLXAPYJCPFBFT-UHFFFAOYSA-L 0.000 description 1
- ZZNKTPQUAXRGHS-UHFFFAOYSA-N CC1=CC(C)([Ti])C(C)=C1C Chemical compound CC1=CC(C)([Ti])C(C)=C1C ZZNKTPQUAXRGHS-UHFFFAOYSA-N 0.000 description 1
- XXAMNASAPGLDCW-UHFFFAOYSA-L CC1=CC(C)=C(C)C1[Zr](Cl)(Cl)(=[Si](C)C)C1C(C)=C(C)C=C1C Chemical compound CC1=CC(C)=C(C)C1[Zr](Cl)(Cl)(=[Si](C)C)C1C(C)=C(C)C=C1C XXAMNASAPGLDCW-UHFFFAOYSA-L 0.000 description 1
- HVWMBQGJDWQRHG-UHFFFAOYSA-L CCC1=CC(C)=C(C)[C@H]1[Zr](Cl)(Cl)([C@@H]1C(C)=C(C)C=C1CC)=[Si](C)C Chemical compound CCC1=CC(C)=C(C)[C@H]1[Zr](Cl)(Cl)([C@@H]1C(C)=C(C)C=C1CC)=[Si](C)C HVWMBQGJDWQRHG-UHFFFAOYSA-L 0.000 description 1
- CKNXPIUXGGVRME-UHFFFAOYSA-L CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 Chemical compound CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 CKNXPIUXGGVRME-UHFFFAOYSA-L 0.000 description 1
- UURNTTJSJYAHOL-UHFFFAOYSA-N C[Si](C)(C)N[Si](C)(C)C.Cl.Cl Chemical compound C[Si](C)(C)N[Si](C)(C)C.Cl.Cl UURNTTJSJYAHOL-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- DZETZMSAJDMAKS-UHFFFAOYSA-L Cl[Zr]Cl.[CH]1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical compound Cl[Zr]Cl.[CH]1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 DZETZMSAJDMAKS-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- XWVDYSRGVSBRDO-UHFFFAOYSA-K [Cl-].[Cl-].C(C)(C)C1=C([O-])C(=CC=C1)C(C)C.CC=1C(=C(C(C1)(C)[Ti+3])C)C Chemical compound [Cl-].[Cl-].C(C)(C)C1=C([O-])C(=CC=C1)C(C)C.CC=1C(=C(C(C1)(C)[Ti+3])C)C XWVDYSRGVSBRDO-UHFFFAOYSA-K 0.000 description 1
- DPYHNFCUYBAQPI-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)[N-]C(C)C.CC=1C(=C(C(C1)(C)[Ti+3])C)C Chemical compound [Cl-].[Cl-].C(C)(C)[N-]C(C)C.CC=1C(=C(C(C1)(C)[Ti+3])C)C DPYHNFCUYBAQPI-UHFFFAOYSA-L 0.000 description 1
- ANSIGMWGPVHUDP-UHFFFAOYSA-L [Cl-].[Cl-].C1(CCCCCCCCCCC1)[N-]C1CCCCCCCCCCC1.CC=1C(=C(C(C1)(C)[Ti+3])C)C Chemical compound [Cl-].[Cl-].C1(CCCCCCCCCCC1)[N-]C1CCCCCCCCCCC1.CC=1C(=C(C(C1)(C)[Ti+3])C)C ANSIGMWGPVHUDP-UHFFFAOYSA-L 0.000 description 1
- NOQWABVRFAHTQD-UHFFFAOYSA-L [Cl-].[Cl-].C12=CC=CCC2CCC1[Zr+2]C1C2=CC=CCC2CC1 Chemical compound [Cl-].[Cl-].C12=CC=CCC2CCC1[Zr+2]C1C2=CC=CCC2CC1 NOQWABVRFAHTQD-UHFFFAOYSA-L 0.000 description 1
- WUHNCOKZAXXSIT-UHFFFAOYSA-L [Cl-].[Cl-].CC1([Zr++]C2(C)C=CC(=C2)C(F)(F)F)C=CC(=C1)C(F)(F)F Chemical compound [Cl-].[Cl-].CC1([Zr++]C2(C)C=CC(=C2)C(F)(F)F)C=CC(=C1)C(F)(F)F WUHNCOKZAXXSIT-UHFFFAOYSA-L 0.000 description 1
- DMWNWKWSNCCZJC-UHFFFAOYSA-L [Cl-].[Cl-].CC1([Zr++]C2(C)C=CC(=C2)[Si](C)(C)C)C=CC(=C1)[Si](C)(C)C Chemical compound [Cl-].[Cl-].CC1([Zr++]C2(C)C=CC(=C2)[Si](C)(C)C)C=CC(=C1)[Si](C)(C)C DMWNWKWSNCCZJC-UHFFFAOYSA-L 0.000 description 1
- OHAVAGOWTCPOEB-UHFFFAOYSA-L [Cl-].[Cl-].CC1([Zr++]C2(C)C=CC(=C2)c2ccccc2)C=CC(=C1)c1ccccc1 Chemical compound [Cl-].[Cl-].CC1([Zr++]C2(C)C=CC(=C2)c2ccccc2)C=CC(=C1)c1ccccc1 OHAVAGOWTCPOEB-UHFFFAOYSA-L 0.000 description 1
- RTNCUOMQMUUQHF-UHFFFAOYSA-L [Cl-].[Cl-].CC1CC2CC=CC=C2C1[Zr+2]C1C2=CC=CCC2CC1C Chemical compound [Cl-].[Cl-].CC1CC2CC=CC=C2C1[Zr+2]C1C2=CC=CCC2CC1C RTNCUOMQMUUQHF-UHFFFAOYSA-L 0.000 description 1
- OUQJXMDGPUPAFO-UHFFFAOYSA-K [Cl-].[Cl-].CC=1C(C(=C(C=1C)C)C)[Ti+2]OC1=CC=CC=C1 Chemical compound [Cl-].[Cl-].CC=1C(C(=C(C=1C)C)C)[Ti+2]OC1=CC=CC=C1 OUQJXMDGPUPAFO-UHFFFAOYSA-K 0.000 description 1
- BMUATHRKSSURHQ-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+3].C[Si](=C1C(CCCCCCCCCC1)[N-]C1(C(=C(C(=C1)C)C)C)C)C Chemical compound [Cl-].[Cl-].[Ti+3].C[Si](=C1C(CCCCCCCCCC1)[N-]C1(C(=C(C(=C1)C)C)C)C)C BMUATHRKSSURHQ-UHFFFAOYSA-L 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Chemical group C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- XGIUDIMNNMKGDE-UHFFFAOYSA-N bis(trimethylsilyl)azanide Chemical compound C[Si](C)(C)[N-][Si](C)(C)C XGIUDIMNNMKGDE-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical group OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052620 chrysotile Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- IVTQDRJBWSBJQM-UHFFFAOYSA-L dichlorozirconium;indene Chemical compound C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C2=CC=CC=C2C=C1 IVTQDRJBWSBJQM-UHFFFAOYSA-L 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- GTLMIIKASNFJDX-UHFFFAOYSA-N diethylalumanylium;dimethylazanide Chemical compound C[N-]C.CC[Al+]CC GTLMIIKASNFJDX-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 229910000269 smectite group Inorganic materials 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000005309 thioalkoxy group Chemical group 0.000 description 1
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical group O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
本発明は、オレフィン重合用触媒成分、オレフィン重合用触媒および該触媒を用いたポリオレフィンの製造方法に関し、更に詳しくは、特定の構造を有するイオン交換性層状珪酸塩を用いることにより、オレフィン重合用触媒の活性が高く、低コストでポリオレフィンの製造を可能にする触媒成分、触媒およびポリオレフィンの製造方法に関する。 The present invention relates to a catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing polyolefin using the catalyst, and more particularly, a catalyst for olefin polymerization by using an ion-exchange layered silicate having a specific structure. The present invention relates to a catalyst component, a catalyst, and a method for producing a polyolefin, which enable the production of a polyolefin at a low cost.
粘土または粘土鉱物をオレフィン重合用触媒成分として利用した触媒の存在下に、オレフィンを重合して、オレフィン重合体を製造することは公知である（例えば、特許文献１参照。）。また、酸処理、塩処理または酸と塩との共存下に処理を行ったイオン交換性層状化合物を成分として含むオレフィン重合触媒も、知られている（例えば、特許文献２〜４参照。）。
さらに、製造するポリマーの粒子性状の改良や反応器や配管へのファウリング防止のために、あらかじめ予備的な重合を行う方法（例えば、特許文献５、６参照。）や、粘土または粘土鉱物を造粒することにより性状の良い重合パウダーを得る方法も、知られている（例えば、特許文献７参照。）。
It is known to produce an olefin polymer by polymerizing an olefin in the presence of a catalyst using clay or clay mineral as a catalyst component for olefin polymerization (see, for example, Patent Document 1). Moreover, the olefin polymerization catalyst which contains as an ingredient the ion exchange layered compound processed in the coexistence of acid treatment, salt treatment, or an acid and a salt is also known (for example, refer patent documents 2-4).
Furthermore, in order to improve the particle properties of the polymer to be produced and to prevent fouling to the reactor and piping, a method of conducting preliminary polymerization in advance (see, for example, Patent Documents 5 and 6), clay or clay mineral A method of obtaining a polymer powder having good properties by granulation is also known (for example, see Patent Document 7).
別の手法として、イオン交換性層状珪酸塩の化学処理において、処理中に処理剤濃度を変更させたイオン交換性層状珪酸塩をオレフィン重合用触媒成分として用いる方法も知られている（例えば、特許文献８参照。）。これは、化学処理中の処理剤濃度を変化することによって、イオン交換性層状珪酸塩の膨潤力が処理中に変化し、化学的および物理的性質を変えることができるため，このようにして製造したイオン交換性層状珪酸塩をオレフィン重合用触媒成分として用いた場合、得られたポリマーの粒子性状が良好になるという思想に基づいている。ここで、イオン交換性層状珪酸塩の膨潤力とは、層間に水分子が配位して、層間が押し広げられる程度のことを意味している。
さらに、イオン交換性層状珪酸塩を含む粘土・粘土鉱物は、溶液中で粘土の微粒子（粘土粒子）として分散や凝集という性質を示す。粘土粒子は、溶液の状態（ｐＨや温度など）によって、膨潤し分散したり、膨潤せずに凝集して沈殿したりする。粘土粒子に対する処理の均一性を考えた場合、処理中に高濃度から低濃度へと変化させることで、粘土粒子は、膨潤し分散状態になり、新たな粘土粒子の端面が発生するが、先に処理された部分が続けて処理されるため、酸処理は、不均一進行しサイズの大きな細孔が増えることにつながる。このような不均一処理は、酸処理による金属成分の溶出が結晶層間や結晶構造内に酸が侵入することと関係しているため、結晶構造が歪んだところから優先されるという現象から予想できる。逆に、低濃度から高濃度へと変化させた場合は、処理途中で粘土粒子は、膨潤しにくくなり凝集する。よって、最初は露出し処理が進行していた端面は、濃度変化による凝集で覆い隠された状態になり、処理は進まなくなってしまう。このように凝集した粘土粒子の表面で処理は、進行し，この場合も、処理は不均一に進行しサイズの大きな細孔が発生することになる。
このようにしてサイズの大きな細孔を作ることで、メタロセン錯体を担持させた場合に、活性点が適度に分散し、重合熱が効率良く分散されることから、ポリマー同士の接着が改善される。一方で，活性向上については，触れていない。
As another technique, in chemical treatment of ion-exchangeable layered silicate, a method is also known in which ion-exchangeable layered silicate whose treatment agent concentration is changed during the treatment is used as a catalyst component for olefin polymerization (for example, patents). Reference 8). This is because the swelling power of the ion-exchanged layered silicate changes during processing by changing the concentration of the processing agent during chemical processing, and thus the chemical and physical properties can be changed. This is based on the idea that when the ion-exchanged layered silicate is used as a catalyst component for olefin polymerization, the resulting polymer has good particle properties. Here, the swelling force of the ion-exchange layered silicate means that the water molecules are coordinated between the layers and the layers are expanded.
Furthermore, clays and clay minerals containing ion-exchange layered silicate exhibit properties of dispersion and aggregation as fine clay particles (clay particles) in solution. Depending on the state of the solution (pH, temperature, etc.), the clay particles swell and disperse, or aggregate and precipitate without swelling. Considering the uniformity of the treatment for clay particles, the clay particles swell and become dispersed by changing from a high concentration to a low concentration during the treatment, and new end faces of the clay particles are generated. Therefore, the acid treatment proceeds non-uniformly and leads to an increase in large-sized pores. Such heterogeneous treatment can be expected from the phenomenon that the elution of the metal component by the acid treatment is related to the invasion of the acid between the crystal layers and the crystal structure, so that the crystal structure is preferentially distorted. . Conversely, when the concentration is changed from a low concentration to a high concentration, the clay particles are less likely to swell during the treatment and aggregate. Therefore, the end face that was initially exposed and processed is covered by aggregation due to the density change, and the processing does not proceed. The treatment proceeds on the surface of the agglomerated clay particles as described above, and in this case, the treatment proceeds non-uniformly and large pores are generated.
By creating large-sized pores in this way, when the metallocene complex is supported, the active sites are appropriately dispersed and the heat of polymerization is efficiently dispersed, so the adhesion between the polymers is improved. . On the other hand, there is no mention of activity improvement.
また、酸処理について着目した技術としては、高い酸濃度により処理したイオン交換性層状珪酸塩をオレフィン重合用触媒成分として用いる方法も知られている（例えば、特許文献９参照。）。これは，高濃度の酸で凝集した粘土粒子を局所的に処理することでサイズの大きな細孔を発生させ、オレフィン重合用触媒成分として用いた場合に、ポリマーの粒子性状を改善することができる。同時に、このような製造方法から作られると、表面積も大きく増加させることができ、触媒活性も向上することが記載されている。 In addition, as a technique paying attention to acid treatment, a method using an ion-exchange layered silicate treated with a high acid concentration as a catalyst component for olefin polymerization is also known (see, for example, Patent Document 9). This is because the clay particles agglomerated with a high concentration of acid are locally treated to generate large-sized pores, which can improve the particle properties of the polymer when used as a catalyst component for olefin polymerization. . At the same time, it is described that when made from such a production method, the surface area can be greatly increased and the catalytic activity is also improved.
さらに、最近では、特定の構造を持つイオン交換性層状珪酸塩を用いることにより、ポリマー同士の付着が少なく、反応器への付着等が改良されることも、知られている（例えば、特許文献１０〜１２参照。）。これらは、ファウリングが起こりやすく製造が困難な低融点ポリマーの重合においても、比較的大きな細孔を持ち、かつ細孔容積が大きいイオン交換性層状珪酸塩を用いることによって、均一に予備重合が進行する触媒系が得られ、嵩密度が高く、凝集量が少ない等、粉体性状の良好な重合ポリマーが得られるというものである。比較実験例として例示されているイオン交換性層状珪酸塩は、比較的小さな細孔を有しているが、化学処理において溶液中のイオン強度が高く、粘土粒子の膨潤力は、限定され、イオン交換性層状珪酸塩の酸処理は、不均一に行われたものとなっており、低活性で、かさ密度は低く、凝集量が多い等、粉体性状の悪い重合ポリマーが得られている。 Furthermore, recently, it is also known that by using an ion-exchange layered silicate having a specific structure, adhesion between polymers is small and adhesion to a reactor is improved (for example, patent document). 10-12)). Even in the polymerization of low melting point polymers which are prone to fouling and difficult to produce, pre-polymerization can be performed uniformly by using ion-exchange layered silicate having relatively large pores and a large pore volume. A proceeding catalyst system is obtained, and a polymer having good powder properties such as a high bulk density and a small amount of aggregation is obtained. The ion-exchange layered silicate exemplified as a comparative experimental example has relatively small pores, but the ionic strength in the solution is high in the chemical treatment, and the swelling power of the clay particles is limited. The acid treatment of the exchangeable layered silicate has been performed unevenly, and a polymer having poor powder properties such as low activity, low bulk density, and a large amount of aggregation has been obtained.
イオン交換性層状珪酸塩は、酸処理によって、表面の不純物が除かれるだけでなく、主として、八面体構造層を構成する原子、例えば、アルミニウムや鉄、マグネシウム等のイオンが溶出し、細孔容積や表面積が増加する。一般的に細孔容積や表面積が増加すると、活性成分の担持量が増加して高い活性を示すことが多い。
しかしながら、これをオレフィン重合用触媒成分として用いた際には、細孔容積や表面積が増加しても、必ずしも高い活性を示さない。上記のようなこれまでの技術だけでは、オレフィン重合用触媒成分について、より高活性な重合用触媒を得るためには、未だ十分でなく、さらなる技術向上が望まれている。
Ion-exchange layered silicate not only removes impurities on the surface by acid treatment, but also mainly elutes atoms that make up the octahedral structure layer, such as aluminum, iron, magnesium, etc. And the surface area increases. In general, when the pore volume or the surface area is increased, the amount of the active ingredient supported is increased and often exhibits high activity.
However, when this is used as a catalyst component for olefin polymerization, even if the pore volume or surface area increases, it does not necessarily show high activity. The above conventional techniques alone are not yet sufficient for obtaining a more highly active polymerization catalyst for the olefin polymerization catalyst component, and further technical improvements are desired.
本発明の目的は、上記従来技術の状況や問題点に鑑み、良好な性状のポリマーを、高活性で得ることができるオレフィン重合用触媒成分、オレフィン重合触媒およびそれを用いたポリオレフィンの製造方法を提供することにある。 An object of the present invention is to provide an olefin polymerization catalyst component, an olefin polymerization catalyst, and a method for producing a polyolefin using the same, which can obtain a polymer having a good property with high activity in view of the situation and problems of the prior art. It is to provide.
本発明者等は、上記目的を達成するために鋭意研究した結果、特定の構造を持ったイオン交換性層状珪酸塩を、オレフィン重合用触媒成分として用いることにより、触媒活性の顕著な向上効果を示すとの知見を得た。さらに、本発明者等は、イオン交換性層状珪酸塩の化学処理を特定のイオン強度にて行い、イオン交換性層状珪酸塩の膨潤力を制御することによる構造変化、特に、八面体構造層を形成する原子の溶出量と細孔容積およびその分布を詳細に検討した結果、イオン交換性層状珪酸塩の持つ細孔のうち、より微小な細孔を多く有するイオン交換性層状珪酸塩をオレフィン重合用触媒成分として使用することによって、活性が顕著に向上することを見出した。本発明は、これらの知見に基づき、完成するに至った。 As a result of diligent research to achieve the above object, the present inventors have used an ion-exchange layered silicate having a specific structure as a catalyst component for olefin polymerization, thereby achieving a significant improvement in catalytic activity. Obtained knowledge to show. Furthermore, the present inventors performed chemical treatment of the ion-exchange layered silicate at a specific ionic strength, and changed the structure by controlling the swelling force of the ion-exchange layered silicate, in particular, the octahedral structure layer. As a result of detailed examination of the elution amount and pore volume of atoms to be formed and their distribution, olefin polymerization of ion-exchanged layered silicates with many finer pores among the pores of ion-exchanged layered silicates It has been found that the activity is remarkably improved by using it as a catalyst component. The present invention has been completed based on these findings.
すなわち、本発明の第１の発明によれば、次の特性１及び特性２を満たすイオン交換性層状珪酸塩からなることを特徴とするオレフィン重合用触媒成分が提供される。
特性１：イオン交換性層状珪酸塩の窒素吸着法により測定した平均細孔径が２〜６ｎｍであること。
特性２：イオン交換性層状珪酸塩の窒素吸着法により測定した細孔径２〜６ｎｍの範囲の微小細孔容積が０．１４ｍｌ／ｇ以上であること。
That is, according to the first aspect of the present invention, there is provided an olefin polymerization catalyst component comprising an ion-exchange layered silicate that satisfies the following characteristics 1 and 2.
Characteristic 1: The average pore diameter measured by the nitrogen adsorption method of the ion-exchange layered silicate is 2 to 6 nm.
Characteristic 2: The micropore volume in the range of pore diameter of 2 to 6 nm measured by the nitrogen adsorption method of ion-exchange layered silicate is 0.14 ml / g or more.
また、本発明の第２の発明によれば、第１の発明において、下記の数式（１）で定義される溶液中のイオン強度が０．０５〜８．００ｍｏｌ／Ｌの条件で化学処理されたものであることを特徴とするオレフィン重合用触媒成分が提供される。
イオン強度（ｍｏｌ／Ｌ）＝０．５×Σ（溶液中のイオンのモル濃度ｍｏｌ／Ｌ×（イオンの電荷数）２）・・・数式（１）
According to the second invention of the present invention, in the first invention, the chemical treatment is performed under the condition that the ionic strength in the solution defined by the following mathematical formula (1) is 0.05 to 8.00 mol / L. The catalyst component for olefin polymerization is provided.
Ionic strength (mol / L) = 0.5 × Σ (mol concentration of ions in solution mol / L × (number of charges of ions) 2 ) (1)
本発明の第３の発明によれば、第１又は２の発明において、前記イオン交換性層状珪酸塩の窒素吸着法により測定したＢＥＴ比表面積が２７０ｍ２／ｇ以上であることを特徴とするオレフィン重合用触媒成分が提供される。
また、本発明の第４の発明によれば、第１〜３のいずれかの発明において、前記イオン交換性層状珪酸塩が酸処理されたものであり、酸処理によってイオン交換性層状珪酸塩の八面体構造層を構成する主金属原子の溶出する割合が１０〜６０％であることを特徴とするオレフィン重合用触媒成分が提供される。
さらに、本発明の第５の発明によれば、第１〜４のいずれかの発明において、前記イオン交換性層状珪酸塩がスメクタイト族の珪酸塩であることを特徴とするオレフィン重合用触媒成分が提供される。
According to a third invention of the present invention, in the first or second invention, the BET specific surface area measured by a nitrogen adsorption method of the ion-exchange layered silicate is 270 m 2 / g or more. A polymerization catalyst component is provided.
According to a fourth invention of the present invention, in any one of the first to third inventions, the ion-exchange layered silicate is acid-treated, and the ion-exchange layered silicate is treated by acid treatment. A catalyst component for olefin polymerization is provided, wherein a ratio of eluting main metal atoms constituting the octahedral structure layer is 10 to 60%.
Furthermore, according to a fifth aspect of the present invention, there is provided an olefin polymerization catalyst component according to any one of the first to fourth aspects, wherein the ion-exchangeable layered silicate is a smectite group silicate. Provided.
また、本発明の第６の発明によれば、下記成分（ａ）、成分（ｂ）および必要に応じて成分（ｃ）からなることを特徴とするオレフィン重合用触媒が提供される。
成分（ａ）：周期率表４〜６族遷移金属のメタロセン化合物
成分（ｂ）：第１〜５のいずれかの発明に係るイオン交換性層状珪酸塩
成分（ｃ）：有機アルミニウム化合物
According to a sixth aspect of the present invention, there is provided an olefin polymerization catalyst characterized by comprising the following component (a), component (b) and, if necessary, component (c).
Component (a): Metallocene compound of a periodic table 4 to 6 transition metal component (b): Ion-exchange layered silicate according to any one of the first to fifth inventions Component (c): Organoaluminum compound
また、本発明の第７の発明によれば、第６の発明に係るオレフィン重合用触媒を使用してオレフィンを重合することを特徴とするポリオレフィンの製造方法が提供される。 According to a seventh aspect of the present invention, there is provided a method for producing a polyolefin, wherein the olefin is polymerized using the olefin polymerization catalyst according to the sixth aspect.
本発明のオレフィン重合用触媒成分を用いることにより、良好な性状のポリオレフィンのポリマーを高活性に製造することができる。 By using the catalyst component for olefin polymerization of the present invention, a polyolefin polymer having good properties can be produced with high activity.
以下、本発明を詳細に説明する。
１．オレフィン重合用触媒成分
本発明のオレフィン重合用触媒成分には、次の特性１及び特性２を有するイオン交換性層状珪酸塩を使用する。
特性１：イオン交換性層状珪酸塩の窒素吸着法により測定した平均細孔径が２〜６ｎｍであること。
特性２：イオン交換性層状珪酸塩の窒素吸着法により測定した細孔径２〜６ｎｍの範囲の微小細孔容積が０．１４ｍｌ／ｇ以上であること。
Hereinafter, the present invention will be described in detail.
1. Olefin Polymerization Catalyst Component For the olefin polymerization catalyst component of the present invention, an ion-exchange layered silicate having the following characteristics 1 and 2 is used.
Characteristic 1: The average pore diameter measured by the nitrogen adsorption method of the ion-exchange layered silicate is 2 to 6 nm.
Characteristic 2: The micropore volume in the range of pore diameter of 2 to 6 nm measured by the nitrogen adsorption method of ion-exchange layered silicate is 0.14 ml / g or more.
ここで窒素吸着法による平均細孔径、細孔容積およびＢＥＴ比表面積の測定方法について、以下に示す。
固体による気体の吸着量は、温度一定の場合、固体と気体が決まれば、吸着相互作用のポテンシャルは、ほぼ一定であると考えることができるので、吸着量は、圧力のみの関数となり、これを一般的に吸着等温線と呼ぶ。吸着ガスを窒素として、液体窒素温度下で吸着等温線を測定した。得られた吸着等温線を用いてＢＥＴ多点法解析を実施し、比表面積を求めた。
ＢＥＴ比表面積は、一般的に相対圧Ｐ／Ｐ０（Ｐ０は大気圧）＝０．０５〜０．３５付近で、良い直線が得られる範囲で解析され、ＢＥＴプロットを確認しながら、解析範囲を決めた。
また、細孔容積は、吸着側及び脱離側吸着等温線を用いて、ＢＪＨ法解析により細孔分布を求めた。求めた細孔容積の範囲は、イオン交換性層状珪酸塩の粒子内細孔であることを考慮して、メソ孔細孔（細孔径２〜５０ｎｍ）を対象とした。尚、細孔の大きさによってミクロ孔、メソ孔、マクロ孔に分けられ、ＩＵＰＡＣでは、直径２ｎｍ以下の細孔をミクロ孔、直径２〜５０ｎｍの細孔をメソ孔、直径５０ｎｍ以上の細孔をマクロ孔と定義している。
Here, methods for measuring the average pore diameter, pore volume, and BET specific surface area by the nitrogen adsorption method are shown below.
The amount of adsorption of gas by a solid is constant, and if the solid and gas are determined, the potential of the adsorption interaction can be considered to be almost constant, so the amount of adsorption is a function of pressure only. Generally called adsorption isotherm. The adsorption isotherm was measured under liquid nitrogen temperature with nitrogen as the adsorption gas. BET multipoint analysis was performed using the obtained adsorption isotherm to determine the specific surface area.
The BET specific surface area is generally analyzed in a range where a good straight line is obtained around relative pressure P / P 0 (P 0 is atmospheric pressure) = 0.05 to 0.35, and analysis is performed while checking the BET plot. Decided the range.
The pore volume was determined by the BJH method analysis using the adsorption side and desorption side adsorption isotherms. The range of the obtained pore volume was mesopore pores (pore diameter 2 to 50 nm) in consideration of the intraparticle pores of the ion-exchange layered silicate. In addition, micropores, mesopores, and macropores are classified according to the size of the pores. In IUPAC, pores with a diameter of 2 nm or less are micropores, pores with a diameter of 2-50 nm are mesopores, and pores with a diameter of 50 nm or more Are defined as macropores.
本発明では、平均細孔径は、細孔構造を円筒形と仮定して、細孔容積とＢＥＴ比表面積から、以下の式に従い、算出した。
（平均細孔径）＝（４×全細孔容積）／（ＢＥＴ多点法による比表面積）
In the present invention, the average pore diameter was calculated from the pore volume and the BET specific surface area according to the following formula, assuming that the pore structure is cylindrical.
(Average pore diameter) = (4 × total pore volume) / (specific surface area by BET multipoint method)
本発明において、イオン交換性層状珪酸塩の窒素吸着法により測定した平均細孔径は、２〜６ｎｍであり、好ましくは４〜６ｎｍである。平均細孔径が２ｎｍ以下になると、金属錯体が担持する部位がなくなってしまうと考えられ、活性が低下する。一方、平均細孔径が６ｎｍを超えると、大きいサイズの細孔が多くなって、触媒の均一な活性化が損なわれ、また、活性点が減少してしまうと考えられ、活性が低下してしまう。
この２〜６ｎｍという大きさは、イオン交換性層状珪酸塩の端面に当たる部分であると考えられる。そのため，凝集体として存在している粒子が、後述する化学処理中に所望のイオン強度の条件によって膨潤、分散し、イオン交換性層状珪酸塩の端面が露出することで、形成されていく細孔を示していると、考えている。
In this invention, the average pore diameter measured by the nitrogen adsorption method of ion-exchange layered silicate is 2-6 nm, Preferably it is 4-6 nm. When the average pore diameter is 2 nm or less, it is considered that there are no sites carried by the metal complex, and the activity decreases. On the other hand, if the average pore diameter exceeds 6 nm, the number of large-sized pores increases, the uniform activation of the catalyst is impaired, and the active point is considered to decrease, resulting in a decrease in activity. .
This size of 2 to 6 nm is considered to be a portion corresponding to the end face of the ion-exchange layered silicate. Therefore, the pores are formed by the particles existing as aggregates being swollen and dispersed under the conditions of desired ionic strength during the chemical treatment described later, and the end faces of the ion-exchange layered silicate are exposed. I think that shows.
また、そのメソ孔細孔のうち、細孔径が２〜６ｎｍの範囲の細孔を微小細孔とした。
本発明では、窒素吸着法により測定したイオン交換性層状珪酸塩の細孔径２〜６ｎｍの範囲の微小細孔容積は、０．１４ｍｌ／ｇ以上であり、好ましくは０．１５ｍｌ／ｇ以上である。上限は、０．４ｍｌ／ｇである。
微小細孔容積が０．１４ｍｌ／ｇより小さいと、活性が低下してしまう。この容量は、大きいほうが好ましいが、大きすぎると、粒子が脆くなって形状を保てなくなり、粉体性状が悪化してしまう。
後述するように、イオン交換性層状珪酸塩を、イオン強度が低い状態で化学処理する工程を設けることで、粘土粒子の端面で均一に金属の溶出が起こるため、細孔径２〜６ｎｍの細孔量が増加し、微小細孔容積を０．１４ｍｌ／ｇ以上にすることができる。このような微小細孔量は、粘土粒子の八面体構造を有する主金属原子の割合を化学処理前後で変化させることによる制御も可能で、酸処理前の含有量に対して、１０〜６０％減少させることが好ましい。
Of the mesoporous pores, those having a pore diameter in the range of 2 to 6 nm were defined as micropores.
In the present invention, the micropore volume in the pore diameter range of 2 to 6 nm of the ion exchange layered silicate measured by the nitrogen adsorption method is 0.14 ml / g or more, preferably 0.15 ml / g or more. . The upper limit is 0.4 ml / g.
When the micropore volume is smaller than 0.14 ml / g, the activity is lowered. This capacity is preferably large, but if it is too large, the particles become brittle and cannot retain their shape, which deteriorates the powder properties.
As will be described later, by providing a step of chemically treating the ion-exchanged layered silicate with a low ionic strength, metal elution occurs uniformly at the end face of the clay particles. The amount is increased and the micropore volume can be increased to 0.14 ml / g or more. The amount of such fine pores can be controlled by changing the ratio of the main metal atoms having an octahedral structure of clay particles before and after chemical treatment, and is 10 to 60% of the content before acid treatment. It is preferable to decrease.
本発明のイオン交換性層状珪酸塩は、上記２つの特性を有することが好ましいが、更に窒素吸着法により測定したイオン交換性層状珪酸塩のＢＥＴ比表面積が２７０ｍ２／ｇ以上である特性を有することがより好ましい。比表面積は、活性種となり得る金属錯体の担持部位を制御し、より大きい方が好ましい。これより小さくなると、活性が低下する。一方、活性に対しては大きいことが好ましいが、大きすぎると、粒子が脆くなって形状を保てなくなり、粉体性状が悪化してしまう。ＢＥＴ比表面積の上限は、４００ｍ２／ｇである。 The ion-exchange layered silicate of the present invention preferably has the above two properties, but further has the property that the BET specific surface area of the ion-exchange layered silicate measured by nitrogen adsorption method is 270 m 2 / g or more. It is more preferable. The specific surface area controls the site of the metal complex that can be an active species and is preferably larger. If it becomes smaller than this, activity will fall. On the other hand, it is preferable that it is large for the activity, but if it is too large, the particles become brittle and cannot keep their shape, and the powder properties deteriorate. The upper limit of the BET specific surface area is 400 m 2 / g.
上記特性を有するイオン交換性層状珪酸塩は、以下の方法によって製造することができる。
本発明に使用されるイオン交換性層状珪酸塩の原料は、イオン結合などによって構成される面が互いに結合力で並行に積み重なった結晶構造を有し、かつ、含有されるイオンが交換可能である珪酸塩化合物をいう。多くのイオン交換性層状珪酸塩は、天然には粘土鉱物の主成分として産出されるため、その以外の夾雑物（石英やクリストバライト等が挙げられる。）が含まれることが多いが、それらを含んでいても良い。
また、本発明のイオン交換性層状珪酸塩は、天然のものに限らず、人工合成物であっても良い。当該、珪酸塩の具体例としては、例えば、「粘土鉱物学」（白水春雄著、朝倉書店、１９９５年）に記載されている次のようなものが挙げられる。
ｉ）１：１層が主要な構成層であるデッカイト、ナクライト、カオリナイト、アノーキサイト、メタハロイサイト、ハロイサイト等のカオリン族、クリソタイル、リザルタイト、アンチゴライト等の蛇紋石族。
ｉｉ）２：１層が主要な構成層であるモンモリロナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト、スチーブンサイト等のスメクタイト族珪酸塩、バーミキュライト等のバーミキュライト族珪酸塩、雲母、イライト、セリサイト、海緑石等の雲母族珪酸塩、アタパルジャイト、セピオライト、パリゴルスカイト、ベントナイト、パイロフィライト、タルク、緑泥石群等。
これらは混合層を形成していてもよい。
The ion-exchangeable layered silicate having the above characteristics can be produced by the following method.
The raw material of the ion-exchange layered silicate used in the present invention has a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other, and the contained ions can be exchanged. A silicate compound. Many ion-exchanged layered silicates are naturally produced as the main component of clay minerals, so other impurities (such as quartz and cristobalite) are often included, but these are included. You can leave.
Moreover, the ion-exchange layered silicate of the present invention is not limited to a natural one, and may be an artificial synthetic product. Specific examples of the silicate include the followings described in “Clay Mineralogy” (Haruo Hakusui, Asakura Shoten, 1995).
i) Kaolin groups such as decaitite, nacrite, kaolinite, anoxite, metahalloysite, and halloysite, and serpentine groups such as chrysotile, risartite, and antigolite, the primary layer of which is 1: 1.
ii) Smectite silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, etc., vermiculite silicates such as vermiculite, mica, illite, sericite, the main component layer of which is 2: 1. Mica group silicates such as sea green stone, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group.
These may form a mixed layer.
これらの中では、膨潤性を有するイオン交換性層状珪酸塩が好ましい。また、主成分が２：１型構造を有するイオン交換性層状珪酸塩がより好ましい。さらに好ましくは、主成分がスメクタイト族珪酸塩であり、特に好ましくは、主成分がモンモリロナイトである。
八面体層を構成する金属の種類としては、アルミニウム、マグネシウム、鉄、チタンなどであり、その含有量は５〜２０ｗｔ％である。他にも微量層間イオン（イオン交換性層状珪酸塩の層間に含有されるイオン）の種類としては、特に限定されないが、リチウム、ナトリウム等の周期律表第１族のアルカリ金属、カルシウム、マグネシウム等の周期律表第２族のアルカリ土類金属等、工業原料として比較的容易にかつ、安価に入手し得る観点から好ましい。
In these, the ion exchange layered silicate which has swelling property is preferable. Further, an ion-exchange layered silicate whose main component has a 2: 1 type structure is more preferable. More preferably, the main component is a smectite silicate, and particularly preferably, the main component is montmorillonite.
As a kind of metal which comprises an octahedron layer, they are aluminum, magnesium, iron, titanium, etc., The content is 5-20 wt%. There are no particular restrictions on the type of trace interlayer ions (ions contained between the layers of the ion-exchange layered silicate), but alkali metals belonging to the first group of the periodic table such as lithium and sodium, calcium, magnesium, etc. From the viewpoint that it can be obtained relatively easily and inexpensively as an industrial raw material, such as an alkaline earth metal of Group 2 of the periodic table.
本発明のイオン交換性層状珪酸塩は、造粒することが可能であり、また好ましい。造粒方法としては、特に制限されないが、好ましい造粒手法としては、撹拌造粒法、噴霧造粒法、転動造粒法、ブリケッティング、コンパクティング、押出造粒法、流動層造粒法、乳化造粒法、液中造粒法、圧縮成型造粒法等が挙げられる。より好ましくは、噴霧乾燥造粒や噴霧冷却造粒、流動層造粒、噴流層造粒、液中造粒、乳化造粒等が挙げられ、特に好ましくは噴霧乾燥造粒や噴霧冷却造粒が挙げられる。 The ion-exchange layered silicate of the present invention can be granulated and is preferred. The granulation method is not particularly limited, but preferred granulation methods include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation Method, emulsion granulation method, submerged granulation method, compression molding granulation method and the like. More preferably, spray drying granulation, spray cooling granulation, fluidized bed granulation, spouted bed granulation, submerged granulation, emulsification granulation, etc. are mentioned, and spray drying granulation and spray cooling granulation are particularly preferable. Can be mentioned.
噴霧造粒を行う場合、原料スラリーの分散媒として、水あるいはメタノール、エタノール、クロロホルム、塩化メチレン、ペンタン、ヘキサン、ヘプタン、トルエン、キシレン等の有機溶媒を用いる。好ましくは水を分散媒として用いる。
球状粒子が得られる噴霧造粒の原料スラリー液中における層状ケイ酸塩の濃度は、０．１〜７０ｗｔ％、好ましくは５〜５０ｗｔ％、特に好ましくは７〜４５ｗｔ％、非常に好ましくは１０〜４０ｗｔ％である。上記濃度の上限を超えると、球状粒子が得られず、また上記濃度の下限を下回ると、造粒体の平均粒径が小さくなりすぎる。球状粒子が得られる噴霧造粒の熱風の入口の温度は、分散媒により異なるが、水を例にとると、８０〜２６０℃、好ましくは１００〜２２０℃で行う。
When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, or xylene is used as a dispersion medium for the raw material slurry. Preferably, water is used as a dispersion medium.
The concentration of the layered silicate in the raw material slurry liquid for spray granulation from which spherical particles are obtained is 0.1 to 70 wt%, preferably 5 to 50 wt%, particularly preferably 7 to 45 wt%, and most preferably 10 to 10 wt%. 40 wt%. When the upper limit of the concentration is exceeded, spherical particles cannot be obtained, and when the concentration is lower than the lower limit of the concentration, the average particle size of the granulated body becomes too small. The temperature at the inlet of hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but when water is taken as an example, the temperature is 80 to 260 ° C, preferably 100 to 220 ° C.
また、造粒の際に、有機物、無機溶媒、無機塩、各種バインダーを用いてもよい。用いられるバインダーとしては、例えば砂糖、デキストローズ、コーンシロップ、ゼラチン、グルー、カルボキシメチルセルロース類、ポリビニルアルコール、水ガラス、塩化マグネシウム、硫酸アルミニウム、塩化アルミニウム、硫酸マグネシウム、アルコール類、グリコール、澱粉、カゼイン、ラテックス、ポリエチレングリコール、ポリエチレンオキシド、タール、ピッチ、アルミナゾル、シリカゲル、アラビアゴム、アルギン酸ソーダ等が挙げられる。
造粒前のイオン交換性層状珪酸塩の形状については、特に制限はなく、天然に産出する形状、人工的に合成した時点の形状でもよいし、また、粉砕、造粒、分級などの操作によって形状を加工したものを用いてもよい。
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcelluloses, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein, Examples thereof include latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, and sodium alginate.
The shape of the ion-exchange layered silicate before granulation is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or by operations such as grinding, granulation, and classification. You may use what processed the shape.
造粒したイオン交換性層状珪酸塩の粒径は、５μｍ以上、１００μｍ以下であり、球状であることが好ましい。５μｍ未満の微粒子が多く存在すると、反応器への付着等が起こりやすく、ポリマー同士の凝集、重合プロセスによってはショートパスあるいは長期滞留の要因となってしまい好ましくない。１００μｍ以上の粗粒子については、閉塞が起こりやすい等の問題が生じるために好ましくない。これらを満たす平均粒径とするために、あるいは平均粒径に対して極度に小さい、または大きい粒径を示す粒子が存在する場合には、分級、分別等により粒径を制御してもよい。 The granulated ion exchange layered silicate has a particle size of 5 μm or more and 100 μm or less, and preferably spherical. If there are many fine particles of less than 5 μm, adhesion to the reactor is likely to occur, and depending on the aggregation of the polymers and the polymerization process, it may cause a short pass or long-term residence, which is not preferable. Coarse particles of 100 μm or more are not preferable because problems such as easy clogging occur. In order to obtain an average particle diameter that satisfies these conditions, or when particles that are extremely small or large with respect to the average particle diameter are present, the particle diameter may be controlled by classification, classification, or the like.
本発明の特性を示すイオン交換性層状珪酸塩は、化学処理を行うことによって製造できる。化学処理には、イオン交換性層状珪酸塩を酸類で処理する酸処理、アルカリ類で処理するアルカリ処理、無機塩類で処理する塩類処理、また、有機物で処理する有機物処理など様々な処理がある。化学処理は、単独でも行って良いし、組み合わせても、また、同時に行っても良い。好ましくは、酸類による酸処理を行った後に、その他の化学処理を行うことが良い。また、化学処理とは、本発明において、特に酸類による処理のことを示し、酸類を含んだ状態で、その他の化学処理を同時に行うことが好ましい。 The ion-exchange layered silicate exhibiting the characteristics of the present invention can be produced by chemical treatment. The chemical treatment includes various treatments such as acid treatment for treating ion-exchange layered silicate with acids, alkali treatment for treatment with alkalis, salt treatment for treatment with inorganic salts, and organic treatment for treatment with organic matter. The chemical treatment may be performed alone, in combination, or simultaneously. Preferably, other chemical treatments are performed after acid treatment with acids. Further, in the present invention, chemical treatment means treatment with acids in particular, and it is preferable to perform other chemical treatments at the same time in a state containing acids.
本発明の特性を示すイオン交換性層状珪酸塩を製造するには、低い濃度の酸、つまりイオン強度が低い状態で化学処理を行い、均一溶出が優先して進行するように、調製する。それは、イオン交換性層状珪酸塩が酸処理される際に、イオン交換性層状珪酸塩が膨潤する状態において、穏やかな条件で酸処理し、膨潤させつつ酸により八面体構造層を構成する金属成分の溶出を均一にさせることによって、本発明のイオン交換性層状珪酸塩の特定の細孔構造が得られるためである。 In order to produce an ion-exchange layered silicate exhibiting the characteristics of the present invention, a chemical treatment is performed in a state of a low concentration of acid, that is, a low ionic strength, so that uniform elution preferentially proceeds. When the ion-exchange layered silicate is acid-treated, the ion-exchange layered silicate swells and is acid-treated under mild conditions. This is because a specific pore structure of the ion-exchangeable layered silicate of the present invention can be obtained by making the elution of the water uniform.
化学処理について、以下，さらに詳しく説明する。
イオン交換性層状珪酸塩は、層間に水分子が配位して膨潤する性質を有する。また、溶液中では、微小な粘土粒子として懸濁し、分散または凝集して存在する。分散と凝集は、主に粘土粒子間のファンデルワールス力と静電反発力に支配され、この２つの力の大小関係によって粒子間に働く力が決まる。粘土粒子が水中に懸濁したときの挙動は、粒子の形態、表面電荷、懸濁液のｐＨなどによって影響され、非常に複雑であるが、基本的には球状粒子の電気二重層に基づいた理論で説明される。
この理論によれば、一般に粘土粒子を分散させるということは、電気二重層の厚みを増加させることにつながり、溶液中のイオン強度を小さくすることが必要となる。逆に、凝集させることは、イオン強度を大きくすることが必要となる。つまり、粘土粒子は、低イオン強度の溶液中では分散した状態となり、そのような状態で化学処理をすることで、凝集しているときには、露出されていない部分も露出し処理されるため、高活性なイオン交換性層状珪酸塩が形成される。さらに、膨潤という現象も、この分散・凝集と同様に、イオン強度が関係しており、高イオン強度下では、層間への水分子の配位は妨げられるため、膨潤しにくくなり、一方、低イオン強度下では、配位しやすい環境となるため、膨潤しやすくなる。
The chemical treatment will be described in more detail below.
The ion-exchange layered silicate has a property that water molecules coordinate with each other and swell. In the solution, it is suspended as fine clay particles and dispersed or aggregated. Dispersion and aggregation are mainly governed by van der Waals force and electrostatic repulsion force between clay particles, and the force acting between particles is determined by the magnitude relationship between these two forces. The behavior of clay particles when suspended in water is influenced by the morphology of the particles, surface charge, pH of the suspension, etc., and is very complex, but is basically based on the electric double layer of spherical particles Explained in theory.
According to this theory, the dispersion of clay particles generally leads to an increase in the thickness of the electric double layer, and it is necessary to reduce the ionic strength in the solution. Conversely, aggregating requires increasing the ionic strength. In other words, clay particles are dispersed in a solution with a low ionic strength, and by chemical treatment in such a state, when they are agglomerated, the unexposed portions are also exposed and processed. An active ion exchange layered silicate is formed. Furthermore, the phenomenon of swelling is also related to the ionic strength, as in this dispersion / aggregation. Under high ionic strength, the coordination of water molecules between layers is hindered, making it difficult to swell. Under the ionic strength, the environment is easy to coordinate, so that it easily swells.
本発明は、上記考えや発明思想に基づき、特定の化学処理条件で製造することのできる平均細孔径が２〜６ｎｍで、細孔径２〜６ｎｍの細孔容量が０．１４ｍＬ／ｇ以上であるイオン交換性層状珪酸塩をオレフィン重合用触媒成分として用いると、従来技術から得られたものよりも、高活性に重合が進行することを見出した。
このような特性を有するイオン交換性層状珪酸塩を製造するには、上述のように化学処理中の粘土粒子の懸濁状態を制御して、粘土粒子が適度に分散および膨潤した状態にすることが必要で、化学処理中の溶液のイオン強度がキー（かぎ）となる。
ここで、イオン強度とは、一般的な理化学辞典などに記載されているように、溶液中に存在するイオンのモル濃度にイオンの電荷数の二乗をかけた総和に、さらに０．５をかけたものとして定義する。つまり、イオン強度は、下記の数式（１）で定義される。例えば、硫酸水溶液であれば、濃度２ｍｏｌ／Ｌの硫酸水溶液におけるイオン強度は、５ｍｏｌ／Ｌとなる。
イオン強度（ｍｏｌ／Ｌ）＝０．５×Σ（溶液中のイオンのモル濃度ｍｏｌ／Ｌ×（イオンの電荷数）２）・・・数式（１）
Based on the above idea and inventive concept, the present invention has an average pore diameter of 2 to 6 nm and a pore volume of 2 to 6 nm of 0.14 mL / g or more that can be produced under specific chemical treatment conditions. It has been found that when ion-exchangeable layered silicate is used as a catalyst component for olefin polymerization, polymerization proceeds with higher activity than that obtained from the prior art.
In order to produce an ion-exchange layered silicate having such characteristics, the clay particles are appropriately suspended and swollen by controlling the suspension state of the clay particles during the chemical treatment as described above. Is necessary, and the ionic strength of the solution during chemical processing is the key.
Here, as described in general physics and chemistry dictionaries, the ionic strength is obtained by multiplying the sum of the molar concentration of ions present in the solution by the square of the number of charges of the ions and multiplying by 0.5. Defined as That is, the ionic strength is defined by the following mathematical formula (1). For example, in the case of a sulfuric acid aqueous solution, the ionic strength in a sulfuric acid aqueous solution having a concentration of 2 mol / L is 5 mol / L.
Ionic strength (mol / L) = 0.5 × Σ (mol concentration of ions in solution mol / L × (number of charges of ions) 2 ) (1)
本発明で好ましい化学処理におけるイオン強度は、０．０５ｍｏｌ／Ｌ以上であり、８．００ｍｏｌ／Ｌ以下である。また、０．７５ｍｏｌ／Ｌ以上、８．００ｍｏｌ／Ｌ以下であることが好ましく、１．００ｍｏｌ／Ｌ以上、７．５０ｍｏｌ／Ｌ以下であることがより好ましく、１．５０ｍｏｌ／Ｌ以上、７．００ｍｏｌ／Ｌ以下であることがさらに好ましい。
イオン強度が低すぎる場合は、処理に時間を要することから、製造効率が低下し、工業的に有用な方法とは言えない。一方，イオン強度が８．００ｍｏｌ／Ｌよりも高い場合は、先に述べたように、溶液中で粘土粒子は、膨潤しにくくなり、さらに凝集するために、不均一処理となり、充分な性能を示すイオン交換性層状珪酸塩を得ることはできない。さらに，もっとも最初におこなう化学処理において、溶液中に酸類を含みイオン強度が上記範囲内にあることが好ましい。
The ionic strength in the chemical treatment preferred in the present invention is 0.05 mol / L or more and 8.00 mol / L or less. Moreover, it is preferable that they are 0.75 mol / L or more and 8.00 mol / L or less, More preferably, they are 1.00 mol / L or more and 7.50 mol / L or less, 1.50 mol / L or more, 7. More preferably, it is 00 mol / L or less.
If the ionic strength is too low, the treatment takes time, so that the production efficiency is lowered and it cannot be said that it is an industrially useful method. On the other hand, when the ionic strength is higher than 8.00 mol / L, as described above, the clay particles in the solution are less likely to swell and further agglomerate, resulting in non-uniform treatment and sufficient performance. The ion-exchangeable layered silicate shown cannot be obtained. Furthermore, in the first chemical treatment, it is preferable that the solution contains acids and the ionic strength is within the above range.
イオン交換性症状ケイ酸塩の化学処理において、酸類で処理する酸処理について、詳しく説明すると、次のようなことが起こる。
イオン交換性層状珪酸塩を酸で処理すると、先ず、交換性陽イオンが溶出し、溶液中に存在する陽イオンと交換が起こり、次いで、結晶構造に影響を与えて分解し、八面体層を構成する金属が溶出していくようになる。
分解の程度は、酸の濃度、処理時間、酸の種類によって異なるが、マグネシウムを多く含むものが一般に大きく、次いで鉄の多いもの、アルミニウムの多いものの順になる。また、結晶度が高く粒子の大きいものほど、分解性が低いが、これは、酸が結晶層間や結晶構造内に侵入することと関係している。
In the chemical treatment of ion-exchange symptom silicate, the acid treatment treated with acids will be described in detail as follows.
When an ion-exchange layered silicate is treated with an acid, first, the exchangeable cation elutes and exchanges with a cation present in the solution, and then decomposes by affecting the crystal structure to form an octahedral layer. The constituent metals are eluted.
The degree of decomposition varies depending on the acid concentration, treatment time, and type of acid, but the one containing a large amount of magnesium is generally large, followed by the one containing a lot of iron and the one containing a lot of aluminum. In addition, the higher the degree of crystallinity and the larger the particle, the lower the decomposability. This is related to the fact that the acid penetrates between the crystal layers and the crystal structure.
また、溶出については、結晶格子の全ての八面体層にミクロな空隙を有する均一な構造が生成すると考えられる均一溶出と、ある特定の部位の金属イオンが溶出して生成した珪酸と層状珪酸塩の複合体が生成する不均一溶出の機構が考えられる。
高濃度な酸によって長時間酸処理を行うと、すなわちイオン強度が高い場合、不均一溶出が優先して進行して、局所的に酸処理が進行したようになり、細孔構造としては、大きな細孔が増加することになる。従来、細孔容積を増加させることを目的とすれば、高濃度で処理することで得られ、製造効率も高いが、本発明の特性を示すイオン交換性層状珪酸塩は、得られない。
In addition, as for elution, uniform elution that is considered to produce a uniform structure with micro voids in all octahedral layers of the crystal lattice, and silicic acid and layered silicate produced by elution of metal ions at a specific site The mechanism of heterogeneous elution generated by the complex is considered.
When acid treatment is performed for a long time with a high concentration of acid, that is, when the ionic strength is high, non-uniform elution preferentially progresses and acid treatment progresses locally, and the pore structure is large. The pores will increase. Conventionally, if the purpose is to increase the pore volume, it is obtained by processing at a high concentration and the production efficiency is high, but an ion-exchange layered silicate exhibiting the characteristics of the present invention cannot be obtained.
酸処理の条件としては、イオン交換性層状珪酸塩の八面体構造層を構成する主金属原子の溶出する速度を小さくする必要がある。温度は、４０〜１００℃がよく、好ましくは５０〜１００℃である。さらに好ましくは、６０〜１００℃である。あまり温度を低下させると、極端に金属成分の溶出速度が低下し、製造効率が低下する。一方、温度を上げ過ぎると、操作上の安全性が低下する。
また、酸処理時の酸濃度（反応系全体重量に対する酸の重量百分率）は、反応温度にも
よるが、３〜２０ｗｔ％がよく、好ましくは５〜１５ｗｔ％、より好ましくは７〜１２ｗｔ％である。濃度が低くなると、金属成分の溶出が進行せず、製造効率が低下する。一方、酸濃度が高いと、平均細孔径の大きい細孔が増加し、微小細孔が減少してしまい、好ましくない。
As the conditions for the acid treatment, it is necessary to reduce the elution rate of main metal atoms constituting the octahedral structure layer of the ion-exchange layered silicate. The temperature is preferably 40 to 100 ° C, and preferably 50 to 100 ° C. More preferably, it is 60-100 degreeC. If the temperature is lowered too much, the elution rate of the metal component is extremely lowered, and the production efficiency is lowered. On the other hand, if the temperature is raised too much, operational safety is reduced.
The acid concentration during acid treatment (percentage of acid relative to the total weight of the reaction system) depends on the reaction temperature, but is preferably 3 to 20 wt%, preferably 5 to 15 wt%, more preferably 7 to 12 wt%. is there. When the concentration is low, the elution of the metal component does not proceed and the production efficiency is lowered. On the other hand, when the acid concentration is high, pores having a large average pore diameter increase and micropores decrease, which is not preferable.
また、イオン交換性層状珪酸塩の濃度は、３〜５０ｗｔ％の範囲で調製できる。好ましくは５〜３０ｗｔ％、さらに好ましくは５〜２０ｗｔ％である。濃度が低くなると、金属成分の溶出が進行せず、製造効率が低下する。一方、濃度が高いと、スラリーの粘度が上昇してしまい、均一に攪拌混合が困難になる。 Moreover, the density | concentration of an ion exchange layered silicate can be prepared in 3-50 wt%. Preferably it is 5-30 wt%, More preferably, it is 5-20 wt%. When the concentration is low, the elution of the metal component does not proceed and the production efficiency is lowered. On the other hand, when the concentration is high, the viscosity of the slurry increases, and uniform stirring and mixing becomes difficult.
酸処理は、複数回に分けて行うことも可能である。
使用する酸化合物は、塩酸、硫酸、硝酸、シュウ酸、安息香酸、ステアリン酸、プロピリオン酸、フマル酸、マレイン酸、フタル酸などの無機酸および有機酸が例示される。その中でも、無機酸が好ましく、塩酸、硝酸、硫酸が好ましい。さらに好ましくは塩酸、硫酸であり、特に好ましくは硫酸である。
The acid treatment can be performed in a plurality of times.
Examples of the acid compound used include inorganic acids and organic acids such as hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, benzoic acid, stearic acid, propionic acid, fumaric acid, maleic acid, and phthalic acid. Among these, inorganic acids are preferable, and hydrochloric acid, nitric acid, and sulfuric acid are preferable. More preferred are hydrochloric acid and sulfuric acid, and particularly preferred is sulfuric acid.
また、造粒前、造粒時に、特定の微粒子状固体化合物をイオン交換性層状珪酸塩に添加することもよく、この場合には、通常の珪酸塩の酸処理と同時に微粒子状固体を溶出させることも目的の一つである。この場合、微粒子状固体は、中性付近の水中では難溶性を示し、酸性水溶液中では、溶解するものを使用することによって、微粒子状固体が存在していた部分を空孔に変えることが可能となる。 It is also possible to add a specific particulate solid compound to the ion-exchange layered silicate before granulation and at the time of granulation. In this case, the particulate solid is eluted simultaneously with the usual silicate acid treatment. That is one of the purposes. In this case, the particulate solid is sparingly soluble in water near neutrality, and in an acidic aqueous solution, it is possible to change the portion where the particulate solid existed into pores by using a material that dissolves. It becomes.
化学処理、特に酸処理によって溶出する八面体構造層を構成する主金属原子の割合は、化学処理前の含有量に対して、１０〜６０％であることが好ましく、より好ましくは２０〜５０％、さらに好ましくは２５〜５０％、特に好ましくは３０〜４５％である。溶出割合が小さいと、細孔容積が小さく、また、比表面積が小さくなってしまう。一方、溶出割合が大きいと、平均細孔径の大きい細孔が増加し、微小細孔が減少してしまい、好ましくない。
ここで、酸などによって溶出する溶出割合とは、酸処理前のイオン交換性層状珪酸塩の八面体層を構成する主金属原子が、酸処理によって溶出する割合を示すが、その算出方法としては、イオン交換性層状珪酸塩の珪素原子に対する八面体層を構成する主金属原子とのモル比を酸処理によって減少する割合として求めたものである。
本発明において、主金属原子とは、モル数が最多の金属原子を指し、具体的には、アルミニウム（Ａｌ）原子、マグネシウム（Ｍｇ）原子などが該当する。
The ratio of the main metal atoms constituting the octahedral structure layer eluted by chemical treatment, particularly acid treatment, is preferably 10 to 60%, more preferably 20 to 50% with respect to the content before chemical treatment. More preferably, it is 25 to 50%, particularly preferably 30 to 45%. When the elution ratio is small, the pore volume is small and the specific surface area is small. On the other hand, when the elution ratio is large, pores having a large average pore diameter increase and micropores decrease, which is not preferable.
Here, the elution ratio eluted by acid or the like indicates the ratio of the main metal atoms constituting the octahedral layer of the ion-exchange layered silicate before acid treatment to be eluted by acid treatment. The molar ratio of the ion-exchangeable layered silicate to the main metal atoms constituting the octahedral layer with respect to silicon atoms is determined as a ratio that decreases by acid treatment.
In the present invention, the main metal atom refers to a metal atom having the largest number of moles, and specifically corresponds to an aluminum (Al) atom, a magnesium (Mg) atom, or the like.
上記化学処理を実施した後に、洗浄することが好ましい。この際、一般的には、水や有機溶媒などの液体を使用する。洗浄および脱水後は、乾燥を行う。一般的には、乾燥温度は１００〜８００℃、好ましくは１５０〜６００℃で実施可能であり、特に好ましくは１５０〜３００℃である。８００℃を超えると、イオン交換性層状珪酸塩の構造破壊を生じるおそれがあるので、好ましくない。
これらのイオン交換性層状珪酸塩は、構造破壊されなくとも乾燥温度により特性が変化するために、用途に応じて乾燥温度を変えることが好ましい。乾燥時間は、通常１分〜２４時間、好ましくは５分〜４時間であり、雰囲気は、乾燥空気、乾燥窒素、乾燥アルゴン、又は減圧下であることが好ましい。乾燥方法に関しては、特に限定されず各種方法で実施可能である。
It is preferable to wash after the chemical treatment. At this time, generally, a liquid such as water or an organic solvent is used. Drying is performed after washing and dehydration. In general, the drying temperature can be 100 to 800 ° C, preferably 150 to 600 ° C, particularly preferably 150 to 300 ° C. If it exceeds 800 ° C., the structure of the ion-exchange layered silicate may be destroyed, which is not preferable.
Since these ion-exchange layered silicates have different characteristics depending on the drying temperature even if they are not structurally destroyed, it is preferable to change the drying temperature depending on the application. The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours, and the atmosphere is preferably dry air, dry nitrogen, dry argon, or under reduced pressure. It does not specifically limit regarding a drying method, It can implement by various methods.
本発明のイオン交換性層状珪酸塩は、膨潤する状態において、穏やかな条件で酸処理し、膨潤させつつ酸で端面を処理することが処理を均一にさせるため、酸処理を施していることが好ましいが、酸処理前、酸処理中または後に、さらに、塩類処理、インターカレーションなどの化学処理を施しても良い。酸処理中に塩を共存させることにより、より酸処理が均一に進行し、好ましい。 The ion-exchange layered silicate of the present invention is subjected to acid treatment in a swollen state under mild conditions, and in order to make the treatment uniform by treating the end face with acid while swelling, Although it is preferable, chemical treatment such as salt treatment and intercalation may be further performed before, during or after the acid treatment. The presence of a salt during the acid treatment is preferable because the acid treatment proceeds more uniformly.
さらに、一般に、イオン交換性層状珪酸塩には、吸着水および層間水が含まれる。本発明においては、これらの吸着水および層間水を除去して使用するのが好ましい。水の除去には、通常、加熱処理が用いられる。その方法は、特に制限されないが、付着水、層間水が残存しないように、また、構造破壊を生じないよう条件を選ぶことが必要である。
加熱時間は０．１時間以上、好ましくは０．２時間以上である。その際、除去した後の水分含有率が、温度２００℃、圧力１ｍｍＨｇの条件下で２時間脱水した場合の水分含有率を０重量％とした時、３重量％以下、好ましくは１重量％以下であることが好ましい。
以上、本発明の特性を示すイオン交換性層状珪酸塩の製造方法を述べてきたが、本発明の特性が得られる製造方法は、上記に限らず、製造することが可能である。
Further, in general, the ion-exchange layered silicate includes adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water before use. For the removal of water, heat treatment is usually used. The method is not particularly limited, but it is necessary to select conditions so that adhering water and interlayer water do not remain and structural destruction does not occur.
The heating time is 0.1 hour or longer, preferably 0.2 hour or longer. At that time, the moisture content after removal is 3% by weight or less, preferably 1% by weight or less when the moisture content is 0% by weight when dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. It is preferable that
As mentioned above, although the manufacturing method of the ion exchange layered silicate which shows the characteristic of this invention has been described, the manufacturing method with which the characteristic of this invention is acquired is not restricted above, It can manufacture.
２．オレフィン重合用触媒
本発明のイオン交換性層状珪酸塩は、オレフィン重合用触媒成分として、好適に用いられる。オレフィン重合用触媒とは、一般的に、チーグラーナッタ触媒やメタロセン触媒などが挙げられる。
本発明では、好適には成分（ａ）、成分（ｂ）および必要に応じて成分（ｃ）を接触させて、オレフィン重合用触媒を調製することがきる。
成分（ａ）：周期率表４〜６族遷移金属のメタロセン化合物
成分（ｂ）：上述したイオン交換性層状珪酸塩
成分（ｃ）：有機アルミニウム化合物
2. Olefin Polymerization Catalyst The ion-exchange layered silicate of the present invention is suitably used as a catalyst component for olefin polymerization. Examples of the olefin polymerization catalyst generally include a Ziegler-Natta catalyst and a metallocene catalyst.
In the present invention, the catalyst for olefin polymerization can be preferably prepared by contacting the component (a), the component (b) and, if necessary, the component (c).
Component (a): Periodic Table Table 4-6 Group Metallocene Compound of Transition Metal Component (b): Ion Exchange Layered Silicate as described above Component (c): Organoaluminum Compound
（１）成分（ａ）
本発明で使用する成分（ａ）の周期率表４〜６族遷移金属のメタロセン化合物は、共役５員環配位子を少なくとも一個有するメタロセン化合物である。かかる遷移金属化合物として好ましいものは、下記一般式（１）〜（４）で表される化合物である。
(1) Component (a)
The metallocene compound of Group 4-6 transition metal of the periodic table of component (a) used in the present invention is a metallocene compound having at least one conjugated 5-membered ring ligand. Preferred as such transition metal compounds are compounds represented by the following general formulas (1) to (4).
上記一般式（１）〜（４）中、ＡおよびＡ’は、置換基を有してもよい共役五員環配位子（同一化合物内においてＡおよびＡ’は同一でも異なっていてもよい）を示し、Ｑは、二つの共役五員環配位子を任意の位置で架橋する結合性基を示し、Ｚは、窒素原子酸素原子、珪素原子、リン原子またはイオウ原子を含む配位子を示し、Ｑ’は、共役五員環配位子の任意の位置とＺを架橋する結合性基を示し、Ｍは、周期律表４〜６族から選ばれる金属原子を示し、ＸおよびＹは、水素原子、ハロゲン原子、炭化水素基、アルコキシ基、アミノ基、リン含有炭化水素基または珪素含有炭化水素基（同一化合物内においてＸ及びＸ’は、同一でも異なっていてもよい。）を示す。 In the above general formulas (1) to (4), A and A ′ are conjugated five-membered ring ligands which may have a substituent (in the same compound, A and A ′ may be the same or different. Q represents a bonding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and Z represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom. Q ′ represents a bonding group that bridges Z with an arbitrary position of the conjugated five-membered ring ligand, M represents a metal atom selected from Groups 4 to 6 in the periodic table, and X and Y Is a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, amino group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group (in the same compound, X and X ′ may be the same or different). Show.
ＡおよびＡ’としては、例えば、シクロペンタジエニル基を挙げることができる。シクロペンタジエニル基は、水素原子を五個有するもの［Ｃ５Ｈ５−］であってもよく、また、その誘導体、すなわちその水素原子のいくつかが置換基で置換されているものであってもよい。
この置換基の例としては、炭素数１〜４０、好ましくは炭素数１〜３０の炭化水素基である。この炭化水素基は、一価の基としてシクロペンタジエニル基と結合していても、また、これが複数存在するときに、その内の２個がそれぞれ他端（ω−端）で結合してシクロペンタジエニルの一部と共に環を形成していてもよい。後者の例としては、２個の置換基がそれぞれω−端で結合して、該シクロペンタジエニル基中の隣接した２個の炭素原子を共有して縮合六員環を形成しているもの、即ちインデニル基、テトラヒドロインデニル基、フルオレニル基、および縮合七員環を形成しているもの、即ちアズレニル基、テトラヒドロアズレニル基が挙げられる。
ＡおよびＡ’で示される共役五員環配位子の好ましい具体的例としては、置換または非置換のシクロペンタジエニル基、インデニル基、フルオレニル基、またはアズレニル基等が挙げられる。この中で、特に好ましいものは、置換または非置換のインデニル基、またはアズレニル基である。
Examples of A and A ′ include a cyclopentadienyl group. The cyclopentadienyl group may be one having five hydrogen atoms [C 5 H 5- ], or a derivative thereof, that is, one in which some of the hydrogen atoms are substituted with substituents. May be.
Examples of this substituent are hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms. Even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, and when there are a plurality of these, two of them are bonded at the other end (ω-end). A ring may be formed together with a part of cyclopentadienyl. As an example of the latter, two substituents are bonded to each other at the ω-end, and two adjacent carbon atoms in the cyclopentadienyl group are shared to form a condensed six-membered ring. That is, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and a group forming a condensed seven-membered ring, that is, an azulenyl group or a tetrahydroazurenyl group.
Preferable specific examples of the conjugated five-membered ring ligand represented by A and A ′ include a substituted or unsubstituted cyclopentadienyl group, indenyl group, fluorenyl group, or azulenyl group. Of these, a substituted or unsubstituted indenyl group or an azulenyl group is particularly preferable.
シクロペンタジエニル基上の置換基としては、前記の炭素数１〜４０、好ましくは炭素数１〜３０の炭化水素基に加え、フッ素、塩素、臭素等のハロゲン原子基、炭素数１〜１２のアルコキシ基、例えば、−Ｓｉ（Ｒ１）（Ｒ２）（Ｒ３）で示される珪素含有炭化水素基、−Ｐ（Ｒ１）（Ｒ２）で示されるリン含有炭化水素基、または−Ｂ（Ｒ１）（Ｒ２）で示されるホウ素含有炭化水素基が挙げられる。これらの置換基が複数ある場合、それぞれの置換基は同一でも異なっていてもよい。上述のＲ１、Ｒ２、Ｒ３は、同一でも異なっていてもよく、炭素数１〜２４、好ましくは炭素数１〜１８のアルキル基を示す。 As the substituent on the cyclopentadienyl group, in addition to the hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, a halogen atom group such as fluorine, chlorine or bromine, or 1 to 12 carbon atoms. For example, a silicon-containing hydrocarbon group represented by -Si (R 1 ) (R 2 ) (R 3 ), a phosphorus-containing hydrocarbon group represented by -P (R 1 ) (R 2 ), or- Examples thereof include a boron-containing hydrocarbon group represented by B (R 1 ) (R 2 ). When there are a plurality of these substituents, each substituent may be the same or different. R 1 , R 2 and R 3 described above may be the same or different and each represents an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms.
さらに、シクロペンタジエニル基上の置換基として、少なくとも１つの第１５〜１６族元素（すなわち、ヘテロ元素）を有しても良い。この場合、ヘテロ元素自身を活性点近傍に、しかも金属と結合、配位することなく存在させて、活性点の性質を向上させようという思想から、第１５〜１６族元素と共役五員環配位子とを結合する原子数が１以下であるメタロセン錯体がさらに好ましい。
第１５〜１６族元素の配位子上の位置は、特に制限は無いが、２位の置換基上に有することが好ましい。さらに好ましくは２位の置換基が、５員又は６員環中に酸素原子、硫黄原子、窒素原子、及びリン原子よりなる群から選択されるヘテロ原子を含有する単環式又は多環式であることが好ましい。また、好ましくはケイ素もしくはハロゲンを含んでもよい炭素数４〜２０のヘテロ芳香族基であり、ヘテロ芳香族基は、５員環構造が好ましく、ヘテロ原子は、酸素原子、硫黄原子、窒素原子が好ましく、酸素原子、硫黄原子がより好ましく、酸素原子がさらに好ましい。
Furthermore, you may have an at least 1 group 15-16 element (namely, hetero element) as a substituent on a cyclopentadienyl group. In this case, from the idea of improving the properties of the active site by allowing the hetero element itself to be present in the vicinity of the active site without bonding or coordination with the metal, a group 15-15 element and a conjugated five-membered ring are formed. A metallocene complex having 1 or less atoms bonding to the ligand is more preferable.
The position of the group 15 to 16 element on the ligand is not particularly limited, but is preferably on the 2-position substituent. More preferably, the 2-position substituent is monocyclic or polycyclic containing a heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom in a 5-membered or 6-membered ring. Preferably there is. Further, it is preferably a heteroaromatic group having 4 to 20 carbon atoms which may contain silicon or halogen, and the heteroaromatic group preferably has a 5-membered ring structure, and the heteroatom is an oxygen atom, a sulfur atom or a nitrogen atom. Preferably, an oxygen atom and a sulfur atom are more preferable, and an oxygen atom is more preferable.
Ｑは、二つの共役五員環配位子間を任意の位置で架橋する結合性基を、Ｑ’は、共役五員環配位子の任意の位置とＺで示される基を架橋する結合性基を表す。
ＱおよびＱ’の具体例としては、次の基が挙げられる。
（イ）メチレン基、エチレン基、イソプロピレン基、フェニルメチルメチレン基、ジフェニルメチレン基、シクロヘキシレン基等のアルキレン基類
（ロ）ジメチルシリレン基、ジエチルシリレン基、ジプロピルシリレン基、ジフェニルシリレン基、メチルエチルシリレン基、メチルフェニルシリレン基、メチル−ｔ−ブチルシリレン基、ジシリレン基、テトラメチルジシリレン基等のシリレン基類
（ハ）ゲルマニウム、リン、窒素、ホウ素あるいはアルミニウムを含む炭化水素基類
Q is a bonding group that bridges between two conjugated five-membered ring ligands at an arbitrary position, and Q ′ is a bond that bridges an arbitrary position of the conjugated five-membered ring ligand with a group represented by Z. Represents a sex group.
Specific examples of Q and Q ′ include the following groups.
(I) Methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, cyclohexylene group and other alkylene groups (b) dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, Silylene groups such as methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisylylene group, etc. (c) Hydrocarbon groups containing germanium, phosphorus, nitrogen, boron or aluminum
さらに、具体的には、（ＣＨ３）２Ｇｅ、（Ｃ６Ｈ５）２Ｇｅ、（ＣＨ３）Ｐ、（Ｃ６Ｈ５）Ｐ、（Ｃ４Ｈ９）Ｎ、（Ｃ６Ｈ５）Ｎ、（Ｃ４Ｈ９）Ｂ、（Ｃ６Ｈ５）Ｂ、（Ｃ６Ｈ５）Ａｌ（Ｃ６Ｈ５Ｏ）Ａｌで示される基等である。好ましいものは、アルキレン基類およびシリレン基類である。 More specifically, (CH 3 ) 2 Ge, (C 6 H 5 ) 2 Ge, (CH 3 ) P, (C 6 H 5 ) P, (C 4 H 9 ) N, (C 6 H 5 ) N, (C 4 H 9 ) B, (C 6 H 5 ) B, (C 6 H 5 ) Al (C 6 H 5 O) Al and the like. Preference is given to alkylene groups and silylene groups.
また、Ｍは、周期律表第４〜６族から選ばれる金属原子遷移金属を、好ましくは周期律表第４属金属原子を示し、具体的にはチタン、ジルコニウム、ハフニウム等である。特に、ジルコニウム、ハフニウムが好ましい。 M represents a metal atom transition metal selected from Groups 4 to 6 of the periodic table, preferably a Group 4 metal atom of the periodic table, specifically titanium, zirconium, hafnium and the like. In particular, zirconium and hafnium are preferable.
Ｚは、窒素原子、酸素原子、ケイ素原子、リン原子またはイオウ原子を含む配位子、水素原子、ハロゲン原子又は炭化水素基を示す。好ましい具体例としては、酸素原子、イオウ原子、炭素数１〜２０、好ましくは炭素数１〜１２のチオアルコキシ基、炭素数１〜４０、好ましくは炭素数１〜１８のケイ素含有炭化水素基、炭素数１〜４０、好ましくは炭素数１〜１８の窒素含有炭化水素基、炭素数１〜４０、好ましくは炭素数１〜１８のリン含有炭化水素基、水素原子、塩素、臭素、炭素数１〜２０の炭化水素基である。 Z represents a ligand, a hydrogen atom, a halogen atom or a hydrocarbon group containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom. Preferable specific examples include an oxygen atom, a sulfur atom, a thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, C1-C40, preferably C1-C18 nitrogen-containing hydrocarbon group, C1-C40, preferably C1-C18 phosphorus-containing hydrocarbon group, hydrogen atom, chlorine, bromine, C1 ˜20 hydrocarbon groups.
ＸおよびＹは、各々水素原子、ハロゲン原子、炭素数１〜２０、好ましくは炭素数１〜１０の炭化水素基、炭素数１〜２０、好ましくは炭素数１〜１０のアルコキシ基、アミノ基、ジフェニルフォスフィノ基等の炭素数１〜２０、好ましくは炭素数１〜１２のリン含有炭化水素基、またはトリメチルシリル基、ビス（トリメチルシリル）メチル基等の炭素数１〜２０、好ましくは炭素数１〜１２のケイ素含有炭化水素基である。ＸとＹは同一でも異なってもよい。これらのうちハロゲン原子、炭素数１〜１０の炭化水素基、および炭素数１〜１２のアミノ基が特に好ましい。 X and Y are each a hydrogen atom, a halogen atom, a C1-C20, preferably a C1-C10 hydrocarbon group, a C1-C20, preferably a C1-C10 alkoxy group, an amino group, 1 to 20 carbon atoms such as a diphenylphosphino group, preferably a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms, or 1 to 20 carbon atoms such as a trimethylsilyl group or a bis (trimethylsilyl) methyl group, preferably 1 to 1 carbon atom. 12 silicon-containing hydrocarbon groups. X and Y may be the same or different. Of these, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an amino group having 1 to 12 carbon atoms are particularly preferable.
一般式（１）で表される化合物としては、例えば、
（１）ビス（メチルシクロペンタジエニル）ジルコニウムジクロリド、
（２）ビス（ｎ−ブチルシクロペンタジエニル）ジルコニウムジクロリド、
（３）ビス（１，３−ジメチルシクロペンタジエニル）ジルコニウムジクロリド、
（４）ビス（１−ｎ−ブチル−３−メチルシクロペンタジエニル）ジルコニウムジクロリド、
（５）ビス（１−メチル−３−トリフルオロメチルシクロペンタジエニル）ジルコニウムジクロリド、
（６）ビス（１−メチル−３−トリメチルシリルシクロペンタジエニル）ジルコニウムジクロリド、
（７）ビス（１−メチル−３−フェニルシクロペンタジエニル）ジルコニウムジクロリド、
（８）ビス（インデニル）ジルコニウムジクロリド、
（９）ビス（テトラヒドロインデニル）ジルコニウムジクロリド、
（１０）ビス（２−メチル−テトラヒドロインデニル）ジルコニウムジクロリド、
等が挙げられる。
As the compound represented by the general formula (1), for example,
(1) bis (methylcyclopentadienyl) zirconium dichloride,
(2) bis (n-butylcyclopentadienyl) zirconium dichloride,
(3) bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
(4) bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride,
(5) bis (1-methyl-3-trifluoromethylcyclopentadienyl) zirconium dichloride,
(6) bis (1-methyl-3-trimethylsilylcyclopentadienyl) zirconium dichloride,
(7) bis (1-methyl-3-phenylcyclopentadienyl) zirconium dichloride,
(8) bis (indenyl) zirconium dichloride,
(9) bis (tetrahydroindenyl) zirconium dichloride,
(10) Bis (2-methyl-tetrahydroindenyl) zirconium dichloride,
Etc.
一般式（２）で表される化合物としては、例えば、
（１）ジメチルシリレンビス｛１−（２−メチル−４−イソプロピル−４Ｈ−アズレニル）｝ジルコニウムジクロリド、
（２）ジメチルシリレンビス｛１−（２−メチル−４−フェニル−４Ｈ−アズレニル）｝ジルコニウムジクロリド、
（３）ジメチルシリレンビス〔１−｛２−メチル−４−（４−フルオロフェニル）−４Ｈ−アズレニル｝〕ジルコニウムジクロリド、
（４）ジメチルシリレンビス［１−｛２−メチル−４−（２，６−ジメチルフェニル）−４Ｈ−アズレニル｝］ジルコニウムジクロリド、
（５）ジメチルシリレンビス｛１−（２−メチル−４，６−ジイソプロピル−４Ｈ−アズレニル）｝ジルコニウムジクロリド、
（６）ジフェニルシリレンビス｛１−（２−メチル−４−フェニル−４Ｈ−アズレニル）｝ジルコニウムジクロリド、
（７）ジメチルシリレンビス｛１−（２−エチル−４−フェニル−４Ｈ−アズレニル）｝ジルコニウムジクロリド、
（８）エチレンビス｛１−［２−メチル−４−（４−ビフェニリル）−４Ｈ−アズレニル］｝ジルコニウムジクロリド、
（９）ジメチルシリレンビス｛１−［２−エチル−４−（２−フルオロ−４−ビフェニリル）−４Ｈ−アズレニル］｝ジルコニウムジクロリド、
（１０）ジメチルシリレンビス｛１−［２−メチル−４−（２’，６’−ジメチル−４−ビフェニリル）−４Ｈ−アズレニル］｝ジルコニウムジクロリド、
（１１）ジメチルシリレン｛１−［２−メチル−４−（４−ビフェニリル）−４Ｈ−アズレニル］｝｛１−［２−メチル−４−（４−ビフェニリル）インデニル］｝ジルコニウムジクロリド、
（１２）ジメチルシリレン｛１−（２−エチル−４−フェニル−４Ｈ−アズレニル）｝｛１−（２−メチル−４，５−ベンゾインデニル）｝ジルコニウムジクロリド、
（１３）ジメチルシリレンビス｛１−（２−エチル−４−フェニル−７−フルオロ−４Ｈ−アズレニル）｝ジルコニウムジクロリド、
（１４）ジメチルシリレンビス｛１−（２−エチル−４−インドリル−４Ｈ−アズレニル）｝ジルコニウムジクロリド、
（１５）ジメチルシリレンビス［１−｛２−エチル−４−（３，５−ビストリフルオロメチルフェニル）−４Ｈ−アズレニル｝］ジルコニウムジクロリド、
（１６）ジメチルシリレンビス｛１−（２−メチル−４−フェニル−４Ｈ−アズレニル）｝ジルコニウムビス（トリフルオロメタンスルホン酸）、
（１７）ジメチルシリレンビス｛１−（２−メチル−４−フェニルインデニル）｝ジルコニウムジクロリド、
（１８）ジメチルシリレンビス｛１−（２−メチル−４，５−ベンゾインデニル）｝ジルコニウムジクロリド、
（１９）ジメチルシリレンビス〔１−｛２−メチル−４−（１−ナフチル）インデニル｝〕ジルコニウムジクロリド、
（２０）ジメチルシリレンビス｛１−（２−メチル−４，６−ジイソプロピルインデニル）｝ジルコニウムジクロリド、
Examples of the compound represented by the general formula (2) include:
(1) Dimethylsilylenebis {1- (2-methyl-4-isopropyl-4H-azurenyl)} zirconium dichloride,
(2) Dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(3) Dimethylsilylenebis [1- {2-methyl-4- (4-fluorophenyl) -4H-azulenyl}] zirconium dichloride,
(4) Dimethylsilylenebis [1- {2-methyl-4- (2,6-dimethylphenyl) -4H-azulenyl}] zirconium dichloride,
(5) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropyl-4H-azurenyl)} zirconium dichloride,
(6) Diphenylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(7) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(8) ethylenebis {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(9) Dimethylsilylenebis {1- [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(10) Dimethylsilylenebis {1- [2-methyl-4- (2 ′, 6′-dimethyl-4-biphenylyl) -4H-azulenyl]} zirconium dichloride,
(11) Dimethylsilylene {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} {1- [2-methyl-4- (4-biphenylyl) indenyl]} zirconium dichloride,
(12) Dimethylsilylene {1- (2-ethyl-4-phenyl-4H-azulenyl)} {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(13) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-7-fluoro-4H-azurenyl)} zirconium dichloride,
(14) Dimethylsilylenebis {1- (2-ethyl-4-indolyl-4H-azurenyl)} zirconium dichloride,
(15) Dimethylsilylenebis [1- {2-ethyl-4- (3,5-bistrifluoromethylphenyl) -4H-azurenyl}] zirconium dichloride,
(16) Dimethylsilylene bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium bis (trifluoromethanesulfonic acid),
(17) Dimethylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(18) Dimethylsilylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(19) Dimethylsilylenebis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(20) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropylindenyl)} zirconium dichloride,
（２１）ジメチルシリレンビス｛１−（２−エチル−４−フェニルインデニル）｝ジルコニウムジクロリド、
（２２）エチレン−１，２−ビス｛１−（２−メチル−４−フェニルインデニル）｝ジルコニウムジクロリド、
（２３）エチレン−１，２−ビス｛１−（２−エチル−４−フェニルインデニル）｝ジルコニウムジクロリド、
（２４）イソプロピリデンビス｛１−（２−メチル−４−フェニルインデニル）｝ジルコニウムジクロリド、
（２５）エチレン−１，２−ビス｛１−（２−メチル−４−フェニル−４Ｈ−アズレニル）｝ジルコニウムジクロリド、
（２６）イソプロピリデンビス｛１−（２−メチル−４−フェニル−４Ｈ−アズレニル）｝ジルコニウムジクロリド、
（２７）ジメチルゲルミレンビス｛１−（２−メチル−４−フェニルインデニル）｝ジルコニウムジクロリド、
（２８）ジメチルゲルミレンビス｛１−（２−エチル−４−フェニルインデニル）｝ジルコニウムジクロリド、
（２９）フェニルホスフィノビス｛１−（２−エチル−４−フェニルインデニル）｝ジルコニウムジクロリド、
（３０）ジメチルシリレンビス［３−（２−フリル）−２，５−ジメチル−シクロペンタジエニル］ジルコニウムジクロリド、
（３１）ジメチルシリレンビス［２−（２−フリル）−３，５−ジメチル−シクロペンタジエニル］ジルコニウムジクロリド、
（３２）ジメチルシリレンビス［２−（２−フリル）−インデニル］ジルコニウムジクロリド、
（３３）ジメチルシリレンビス［２−（２−（５−メチル）フリル）−４，５−ジメチル−シクロペンタジエニル］ジルコニウムジクロリド、
（３４）ジメチルシリレンビス［２−（２−（２−（５−トリメチルシリル）フリル）−４，５−ジメチル−シクロペンタジエニル）ジルコニウムジクロリド、
（３５）ジメチルシリレンビス［２−（２−チエニル）−インデニル］ジルコニウムジクロリド、
（３６）ジメチルシリレン［２−（２−（５−メチル）フリル）−４−フェニルインデニル］［２−メチル−４−フェニルインデニル］ジルコニウムジクロリド、
（３７）ジメチルシリレンビス（２，３，５−トリメチルシクロペンタジエニル）ジルコニウムジクロリド、
（３８）ジメチルシリレンビス（２，３−ジメチル−５−エチルシクロペンタジエニル）ジルコニウムジクロリド、
（３９）ジメチルシリレンビス（２，５−ジメチル−３−フェニルシクロペンタジエニル）ジルコニウムジクロリド、
等が挙げられる。
(21) Dimethylsilylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(22) ethylene-1,2-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(23) ethylene-1,2-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(24) isopropylidenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(25) ethylene-1,2-bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(26) isopropylidenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(27) Dimethylgermylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(28) Dimethylgermylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(29) phenylphosphinobis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(30) Dimethylsilylenebis [3- (2-furyl) -2,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(31) Dimethylsilylenebis [2- (2-furyl) -3,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(32) Dimethylsilylenebis [2- (2-furyl) -indenyl] zirconium dichloride,
(33) Dimethylsilylenebis [2- (2- (5-methyl) furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(34) Dimethylsilylenebis [2- (2- (2- (5-trimethylsilyl) furyl) -4,5-dimethyl-cyclopentadienyl) zirconium dichloride,
(35) Dimethylsilylenebis [2- (2-thienyl) -indenyl] zirconium dichloride,
(36) Dimethylsilylene [2- (2- (5-methyl) furyl) -4-phenylindenyl] [2-methyl-4-phenylindenyl] zirconium dichloride,
(37) Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
(38) Dimethylsilylenebis (2,3-dimethyl-5-ethylcyclopentadienyl) zirconium dichloride,
(39) Dimethylsilylenebis (2,5-dimethyl-3-phenylcyclopentadienyl) zirconium dichloride,
Etc.
一般式（３）で表される化合物としては、例えば、
（１）（テトラメチルシクロペンタジエニル）チタニウム（ビスｔ−ブチルアミド）ジクロリド、
（２）（テトラメチルシクロペンタジエニル）チタニウム（ビスイソプロピルアミド）ジクロリド、
（３）（テトラメチルシクロペンタジエニル）チタニウム（ビスシクロドデシルアミド）ジクロリド、
（４）（テトラメチルシクロペンタジエニル）チタニウム｛ビス（トリメチルシリル）アミド）｝ジクロリド、
（５）（２−メチル−４−フェニル−４Ｈ−アズレニル）チタニウム｛ビス（トリメチルシリル）アミド｝ジクロリド、
（６）（２−メチルインデニル）チタニウム（ビスｔ−ブチルアミド）ジクロリド、
（７）（フルオレニル）チタニウム（ビスｔ−ブチルアミド）ジクロリド、
（８）（３，６−ジイソプロピルフルオレニル）チタニウム（ビスｔ−ブチルアミド）ジクロリド、
（９）（テトラメチルシクロペンタジエニル）チタニウム（フェノキシド）ジクロリド、
（１０）（テトラメチルシクロペンタジエニル）チタニウム（２，６−ジイソプロピルフェノキシド）ジクロリド、
等が挙げられる。
Examples of the compound represented by the general formula (3) include:
(1) (tetramethylcyclopentadienyl) titanium (bis t-butylamide) dichloride,
(2) (tetramethylcyclopentadienyl) titanium (bisisopropylamide) dichloride,
(3) (tetramethylcyclopentadienyl) titanium (biscyclododecylamide) dichloride,
(4) (Tetramethylcyclopentadienyl) titanium {bis (trimethylsilyl) amide)} dichloride,
(5) (2-Methyl-4-phenyl-4H-azurenyl) titanium {bis (trimethylsilyl) amide} dichloride,
(6) (2-methylindenyl) titanium (bis t-butylamide) dichloride,
(7) (fluorenyl) titanium (bis t-butylamide) dichloride,
(8) (3,6-diisopropylfluorenyl) titanium (bis t-butylamide) dichloride,
(9) (Tetramethylcyclopentadienyl) titanium (phenoxide) dichloride,
(10) (tetramethylcyclopentadienyl) titanium (2,6-diisopropylphenoxide) dichloride,
Etc.
一般式（４）で表される化合物としては、例えば、
（１）ジメチルシランジイル（テトラメチルシクロペンタジエニル）（ｔ−ブチルアミド）チタニウムジクロリド、
（２）ジメチルシランジイル（テトラメチルシクロペンタジエニル）（シクロドデシルアミド）チタニウムジクロリド、
（３）ジメチルシランジイル（２−メチルインデニル）（ｔ−ブチルアミド）チタニウムジクロリド、
（４）ジメチルシランジイル（フルオレニル）（ｔ−ブチルアミド）チタニウムジクロリド、等が挙げられる。
Examples of the compound represented by the general formula (4) include:
(1) Dimethylsilanediyl (tetramethylcyclopentadienyl) (t-butylamido) titanium dichloride,
(2) Dimethylsilanediyl (tetramethylcyclopentadienyl) (cyclododecylamide) titanium dichloride,
(3) Dimethylsilanediyl (2-methylindenyl) (t-butylamido) titanium dichloride,
(4) Dimethylsilanediyl (fluorenyl) (t-butylamido) titanium dichloride, and the like.
本発明で使用する遷移金属化合物としては、一般式（２）で示される化合物が好ましく、さらに、置換基に縮合七員環を形成しているもの、即ちアズレニル基、テトラヒドロアズレニル基を有する化合物が特に好ましい。
なお、一般式（１）〜（４）で示される遷移金属化合物は、同一の一般式で示される化合物および／または異なる一般式で表される化合物の二種以上の混合物として用いることができる。
これらの例示化合物のジクロリドは、ジブロマイド、ジフルオライド、ジメチル、ジフェニル、ジベンジル、ビスジメチルアミド、ビスジエチルアミド等に置き換えた化合物も、同様に例示される。さらに、例示化合物中のジルコニウム、チタニウムは、ハフニウムに置き換えた化合物も、同様に、例示される。
As the transition metal compound used in the present invention, a compound represented by the general formula (2) is preferable, and a compound having a condensed seven-membered ring as a substituent, that is, a compound having an azulenyl group or a tetrahydroazurenyl group. Is particularly preferred.
The transition metal compounds represented by the general formulas (1) to (4) can be used as a mixture of two or more compounds represented by the same general formula and / or compounds represented by different general formulas.
The compounds in which the dichlorides of these exemplified compounds are replaced with dibromide, difluoride, dimethyl, diphenyl, dibenzyl, bisdimethylamide, bisdiethylamide and the like are also exemplified. Furthermore, compounds in which zirconium and titanium in the exemplified compounds are replaced with hafnium are also exemplified.
（２）成分（ｃ）
成分（ｃ）は、有機アルミニウム化合物である。
本発明で成分（ｃ）として用いられる有機アルミニウム化合物は、一般式：（ＡｌＲｎＸ３−ｎ）ｍ で表される有機アルミニウム化合物が使用される。式中、Ｒは、炭素数１〜２０のアルキル基を表し、Ｘは、ハロゲン、水素、アルコキシ基又はアミノ基を表し、ｎは１〜３の、ｍは１〜２の整数を各々表す。有機アルミニウム化合物は、単独であるいは複数種を組み合わせて使用することができる。
(2) Component (c)
Component (c) is an organoaluminum compound.
As the organoaluminum compound used as the component (c) in the present invention, an organoaluminum compound represented by the general formula: (AlR n X 3-n ) m is used. In formula, R represents a C1-C20 alkyl group, X represents a halogen, hydrogen, an alkoxy group, or an amino group, n represents 1-3, m represents the integer of 1-2, respectively. The organoaluminum compounds can be used alone or in combination.
有機アルミニウム化合物の具体例としては、トリメチルアルミニウム、トリエチルアルミニウム、トリノルマルプロピルアルミニウム、トリノルマルブチルアルミニウム、トリイソブチルアルミニウム、トリノルマルヘキシルアルミニウム、トリノルマルオクチルアルミニウム、トリノルマルデシルアルミニウム、ジエチルアルミニウムクロライド、ジエチルアルミニウムセスキクロライド、ジエチルアルミニウムヒドリド、ジエチルアルミニウムエトキシド、ジエチルアルミニウムジメチルアミド、ジイソブチルアルミニウムヒドリド、ジイソブチルアルミニウムクロライド等が挙げられる。
これらのうち、好ましくは、ｍ＝１、ｎ＝３のトリアルキルアルミニウム及びアルキルアルミニウムヒドリドである。さらに好ましくは、Ｒが炭素数１〜８であるトリアルキルアルミニウムである。
Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride.
Of these, trialkylaluminum and alkylaluminum hydride with m = 1 and n = 3 are preferable. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.
（３）オレフィン重合用触媒の調製
本発明のオレフィン重合用触媒は、成分（ａ）と成分（ｂ）及び必要に応じて成分（ｃ）を接触させて、触媒とする。
その接触方法は、特に限定されないが、以下のような順序で接触させることができる。また、この接触は、触媒調製時だけでなく、オレフィンによる予備重合時またはオレフィンの重合時に行ってもよい。これらの接触において、接触を充分に行うため溶媒を用いてもよい。溶媒としては、脂肪族飽和炭化水素、芳香族炭化水素、脂肪族不飽和炭化水素やこれらのハロゲン化物、また予備重合モノマーなどが例示される。
（ｉ）成分（ａ）と成分（ｂ）を接触させる。
（ｉｉ）成分（ａ）と成分（ｂ）を接触させた後に、成分（ｃ）を添加する。
（ｉｉｉ）成分（ｂ）と成分（ｃ）を接触させた後に、成分（ａ）を添加する。
（ｉｖ）成分（ａ）と成分（ｃ）を接触させた後に、成分（ｂ）を添加する。
その他、三成分を同時に接触させてもよい。
(3) Preparation of Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention is made by contacting component (a), component (b) and, if necessary, component (c).
Although the contact method is not specifically limited, Contact can be made in the following order. Further, this contact may be performed not only at the time of catalyst preparation but also at the time of preliminary polymerization with olefin or at the time of polymerization of olefin. In these contacts, a solvent may be used for sufficient contact. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers.
(I) The component (a) is contacted with the component (b).
(Ii) After contacting the component (a) and the component (b), the component (c) is added.
(Iii) Component (b) and component (c) are contacted and then component (a) is added.
(Iv) Component (a) and component (c) are contacted, and then component (b) is added.
In addition, you may contact three components simultaneously.
好ましい接触方法は、成分（ｂ）と成分（ｃ）を接触させた後、未反応の成分（ｃ）を洗浄等で除去し、その後再度必要最小限の成分（ｃ）を成分（ｂ）に接触させ、その後、成分（ａ）を接触させる方法である。この場合のＡｌ／遷移金属のモル比は、０．１〜１，０００、好ましくは２〜１０、さらに好ましくは４〜６の範囲である。 A preferred contact method is to contact the component (b) with the component (c), then remove the unreacted component (c) by washing or the like, and then convert the necessary minimum component (c) to the component (b) again. It is the method of making it contact, and making a component (a) contact after that. In this case, the Al / transition metal molar ratio is in the range of 0.1 to 1,000, preferably 2 to 10, and more preferably 4 to 6.
成分（ｂ）と成分（ｃ）を接触させる（その場合、成分（ａ）が存在していても良い）温度は、０℃〜１００℃が好ましく、さらに好ましくは２０〜８０℃、特に好ましくは３０〜６０℃である。この範囲より低い場合は、反応が遅く、また、高い場合は、成分（ａ）の分解反応が進行するという欠点がある。
また、成分（ａ）と成分（ｃ）を接触させる（その場合、成分（ｂ）が存在していても良い）場合には、有機溶媒を溶媒として存在させることが好ましい。この場合の成分（ａ）の有機溶媒中での濃度は、高い方が好ましい。好ましい成分（ａ）の有機溶媒中での濃度の下限は、好ましくは３ｍｍｏｌ／Ｌ、より好ましくは４ｍｍｏｌ／Ｌ、さらに好ましくは６ｍｍｏｌ／Ｌである。下限を超えると、反応が遅く、十分に反応が進行しないおそれがある。
成分（ｂ）１ｇにつき、遷移金属錯体が０．００１〜１０ｍｍｏｌ、好ましくは０．００１〜１ｍｍｏｌの範囲である。
成分（ｂ）は、酸点を持つことが好ましい。好ましい酸点の量の下限は、成分（ｂ）１ｇにつきｐＫａ＜−８．２以下の強酸点が３０μｍｏｌ、より好ましくは５０μｍｏｌ、さらに好ましくは１００μｍｏｌ、特に好ましくは１５０μｍｏｌである。酸点の量は、特開２０００−１５８７０７号公報の記載の方法に従い、測定する。
The temperature at which the component (b) and the component (c) are brought into contact (in which case the component (a) may be present) is preferably 0 ° C to 100 ° C, more preferably 20 to 80 ° C, and particularly preferably 30-60 ° C. When it is lower than this range, the reaction is slow, and when it is high, the decomposition reaction of component (a) proceeds.
Moreover, when a component (a) and a component (c) are made to contact (in that case component (b) may exist), it is preferable to make an organic solvent exist as a solvent. In this case, the concentration of component (a) in the organic solvent is preferably higher. The lower limit of the concentration of the component (a) in the organic solvent is preferably 3 mmol / L, more preferably 4 mmol / L, still more preferably 6 mmol / L. If the lower limit is exceeded, the reaction is slow and the reaction may not proceed sufficiently.
The transition metal complex is in the range of 0.001 to 10 mmol, preferably 0.001 to 1 mmol per 1 g of component (b).
The component (b) preferably has an acid point. The lower limit of the amount of the acid point is preferably 30 μmol, more preferably 50 μmol, still more preferably 100 μmol, and particularly preferably 150 μmol of the strong acid point of pKa <−8.2 or less per 1 g of the component (b). The amount of acid sites is measured according to the method described in JP 2000-158707 A.
これらは、重合槽内で、あるいは重合槽外で接触させ、オレフィンの存在下で予備重合を行ってもよい。オレフィンとは、炭素間二重結合を少なくとも１個含む炭化水素をいい、エチレン、プロピレン、１−ブテン、１−ヘキセン、３−メチルブテン−１、スチレン、ジビニルベンゼン等が例示されるが、特に種類に制限はなく、これらと他のオレフィンとの混合物を用いてもよい。好ましくは炭素数３以上のオレフィンがよい。 These may be contacted in the polymerization tank or outside the polymerization tank, and the prepolymerization may be performed in the presence of the olefin. Olefin means a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene, and the like. There is no restriction | limiting, You may use the mixture of these and another olefin. An olefin having 3 or more carbon atoms is preferable.
また、本発明の触媒は、粒子性の改良のために、予めオレフィンを接触させて少量重合されることからなる予備重合処理に付すことが好ましい。使用するオレフィンは、特に限定はないが、エチレン、プロピレン、１−ブテン、１−ヘキセン、１−オクテン、４−メチル−１−ペンテン、３−メチル−１−ブテン、ビニルシクロアルカン、スチレンなどを使用することが可能であり、特にプロピレンを使用することが好ましい。
オレフィンの供給方法は、オレフィンを反応槽に定速的にあるいは定圧状態になるように維持する供給方法やその組み合わせ、段階的な変化をさせるなど、任意の方法が可能である。
In addition, the catalyst of the present invention is preferably subjected to a prepolymerization treatment in which a small amount of polymer is brought into contact with an olefin in advance to improve particle properties. The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like can be used. It is possible to use, and it is particularly preferable to use propylene.
The olefin can be supplied by any method, such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.
予備重合時間は、特に限定されないが、５分〜２４時間の範囲であることが好ましい。また、予備重合量は、予備重合ポリマー量が、成分（ｂ）１ｇに対し、好ましくは０．０１〜１００ｇ、さらに好ましくは０．１〜５０ｇである。予備重合を終了した後に、触媒の使用形態に応じ、そのまま使用することが可能であるが、必要ならば乾燥を行ってもよい。
また、予備重合温度は、特に制限は無いが、０℃〜１００℃が好ましく、より好ましくは１０〜７０℃、特に好ましくは２０〜６０℃、さらに好ましくは３０〜５０℃である。この範囲を下回ると、反応速度が低下したり、活性化反応が進行しないという弊害が生じる可能性があり、一方、上回ると、予備重合ポリマーが溶解したり、予備重合速度が速すぎて粒子性状が悪化したり、副反応のため活性点が失活するという弊害が生じる可能性がある。
The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. The amount of prepolymerization is preferably 0.01 to 100 g, more preferably 0.1 to 50 g, based on 1 g of the component (b). After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst, but may be dried if necessary.
The prepolymerization temperature is not particularly limited, but is preferably 0 ° C to 100 ° C, more preferably 10 to 70 ° C, particularly preferably 20 to 60 ° C, and further preferably 30 to 50 ° C. Below this range, the reaction rate may decrease or the activation reaction may not proceed. May be adversely affected or the active site may be deactivated due to side reactions.
予備重合時には、有機溶媒等の液体中で実施することもでき、かつこれが好ましい。予備重合時の固体触媒の濃度には、特に制限は無いが、好ましくは５０ｇ／Ｌ以上、より好ましくは６０ｇ／Ｌ以上、特に好ましくは７０ｇ／Ｌ以上である。濃度が高い方がメタロセンの活性化が進行し、高活性触媒となる。
さらに、上記各成分の接触の際、もしくは接触の後に、ポリエチレン、ポリプロピレン、ポリスチレンなどの重合体やシリカ、チタニアなどの無機酸化物固体を共存させることも可能である。
The preliminary polymerization can be carried out in a liquid such as an organic solvent, and this is preferable. The concentration of the solid catalyst during the prepolymerization is not particularly limited, but is preferably 50 g / L or more, more preferably 60 g / L or more, and particularly preferably 70 g / L or more. The higher the concentration, the more active the metallocene and the higher the activity of the catalyst.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.
予備重合後に触媒を乾燥してもよい。乾燥方法には、特に制限は無いが、減圧乾燥や加熱乾燥、乾燥ガスを流通させることによる乾燥などが例示され、これらの方法を単独で用いてもよいし、２つ以上の方法を組み合わせて用いてもよい。乾燥工程において触媒を攪拌、振動、流動させてもよいし、静置させてもよい。 The catalyst may be dried after the prepolymerization. The drying method is not particularly limited, and examples include drying under reduced pressure, drying by heating, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. It may be used. In the drying step, the catalyst may be stirred, vibrated or fluidized, or may be allowed to stand.
３．ポリオレフィンの製造方法
前記成分（ａ）、成分（ｂ）、及び必要に応じて用いられる成分（ｃ）からなるオレフィン重合用触媒を用いて行う重合は、オレフィン単独あるいは該オレフィンと他のコモノマーとを混合接触させることにより、行われる。
共重合の場合、反応系中の各モノマーの量比は、経時的に一定である必要はなく、各モノマーを一定の混合比で供給することも可能であるし、供給するモノマーの混合比を経時的に変化させることも可能である。また、共重合反応比を考慮してモノマーのいずれかを分割添加することもできる。
3. Production Method of Polyolefin Polymerization carried out using an olefin polymerization catalyst comprising the component (a), the component (b), and the component (c) used as necessary is performed by olefin alone or the olefin and another comonomer. This is done by mixing contact.
In the case of copolymerization, the amount ratio of each monomer in the reaction system does not need to be constant over time, and it is possible to supply each monomer at a constant mixing ratio. It is also possible to change with time. Also, any of the monomers can be added in portions in consideration of the copolymerization reaction ratio.
重合し得るオレフィンとしては、炭素数２〜２０程度のものが好ましく、具体的にはエチレン、プロピレン、１−ブテン、１−ヘキセン、１−オクテン、スチレン、ジビニルベンゼン、７−メチル−１，７−オクタジエン、シクロペンテン、ノルボルネン、エチリデンノルボルネン等が挙げられる。好ましくは炭素数２〜８のα−オレフィンである。共重合の場合、用いられるコモノマーの種類は、前記オレフィンとして挙げられるものの中から、主成分となるもの以外のオレフィンを選択して用いることができる。 As the olefin that can be polymerized, those having about 2 to 20 carbon atoms are preferred. Specifically, ethylene, propylene, 1-butene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1,7 -Octadiene, cyclopentene, norbornene, ethylidene norbornene and the like. Preferred is an α-olefin having 2 to 8 carbon atoms. In the case of copolymerization, the type of comonomer used can be selected from olefins other than the main component from those mentioned as the olefin.
重合様式は、触媒成分と各モノマーが効率よく接触するならば、あらゆる様式を採用しうる。具体的には、不活性溶媒を用いるスラリー法、不活性溶媒を実質的に用いずプロピレンを溶媒として用いる方法、溶液重合法あるいは実質的に液体溶媒を用いず各モノマーをガス状に保つ気相法などが採用できる。また、連続重合、回分式重合、又は予備重合を行う方法も適用される。
スラリー重合の場合は、重合溶媒として、ヘキサン、ヘプタン、ペンタン、シクロヘキサン、ベンゼン、トルエン等の飽和脂肪族又は芳香族炭化水素の単独又は混合物が用いられる。重合温度は、０〜１５０℃であり、また、分子量調節剤として補助的に水素を用いることができる。重合圧力は、０〜２０００ｋｇ／ｃｍ２Ｇ、好ましくは０〜６０ｋｇ／ｃｍ２Ｇが適当である。
As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer come into contact efficiently. Specifically, a slurry method using an inert solvent, a method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or a gas phase in which each monomer is kept in a gaseous state without substantially using a liquid solvent. Laws can be adopted. Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.
In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent. The polymerization temperature is 0 to 150 ° C., and hydrogen can be used as an auxiliary molecular weight regulator. The polymerization pressure is suitably 0 to 2000 kg / cm 2 G, preferably 0 to 60 kg / cm 2 G.
次に、本発明を実施例によって具体的に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、物性測定に使用した分析機器および測定方法は、以下の通りである。
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples.
The analytical instruments and measurement methods used for measuring physical properties are as follows.
（各種物性測定法）
（１）イオン交換性層状珪酸塩の組成分析：
ＪＩＳ法による化学分析により検量線を作成し、蛍光Ｘ線測定にて定量した。
（２）細孔測定および比表面積測定：
窒素吸脱着法による細孔分布および比表面積を測定した。液体窒素温度下で吸着等温線を測定した。得られた吸着側等温線を用いてＢＥＴ多点法解析を実施し、比表面積を求めた。吸着側および脱離側吸着等温線を用いて、ＢＪＨ法解析によりメソ孔細孔分布を求め、メソ細孔容積および微小細孔容積を求めた。
装置：カンタークローム社製オートソーブ３Ｂ
測定手法：窒素ガス吸着法
前処理条件：試料を２００℃、真空下（１．３ＭＰａ以下）で２時間減圧加熱
試料量：約０．２ｇ
ガス液化温度：７７Ｋ
(Various physical property measurement methods)
(1) Composition analysis of ion-exchange layered silicate:
A calibration curve was prepared by chemical analysis by the JIS method and quantified by fluorescent X-ray measurement.
(2) Pore measurement and specific surface area measurement:
The pore distribution and specific surface area were measured by nitrogen adsorption / desorption method. The adsorption isotherm was measured under liquid nitrogen temperature. Using the obtained adsorption side isotherm, BET multipoint analysis was performed to determine the specific surface area. Using adsorption side and desorption side adsorption isotherms, mesopore pore distribution was determined by BJH analysis, and mesopore volume and micropore volume were determined.
Equipment: Autosorb 3B manufactured by Canterchrome
Measurement method: Nitrogen gas adsorption method Pretreatment condition: Sample is heated under reduced pressure at 200 ° C. under vacuum (1.3 MPa or less) for 2 hours. Sample amount: Approximately 0.2 g
Gas liquefaction temperature: 77K
（３）粒径分布の測定：
堀場製作所社製レーザー回折・散乱式粒子径分布測定装置ＬＡ−９２０を用い、分散溶媒をエタノール、屈折率１．３、形状係数１．０の条件で測定した。
（４）ＭＦＲ（メルトマスフローレート）：
タカラ社製メルトインデクサーを用い、ＪＩＳ Ｋ７２１０の「プラスチック―熱可塑性プラスチックのメルトマスフローレート（ＭＦＲ）及びメルトボリュームフローレート（ＭＶＲ）の試験方法」の試験条件：２３０℃、２．１６ｋｇ荷重に準拠して、測定した。
（５）ポリマー嵩密度：
重合体（ポリマー）の嵩密度（ＢＤ）をＡＳＴＭ Ｄ１８９５−６９に準ずる装置を使用し、測定した。
(3) Measurement of particle size distribution:
Using a laser diffraction / scattering particle size distribution measuring apparatus LA-920 manufactured by HORIBA, Ltd., the dispersion solvent was measured under the conditions of ethanol, refractive index 1.3, and shape factor 1.0.
(4) MFR (melt mass flow rate):
Using Takara's melt indexer, JIS K7210 "Plastics-Testing methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics": compliant with 230 ° C, 2.16 kg load And measured.
(5) Polymer bulk density:
The bulk density (BD) of the polymer (polymer) was measured using an apparatus according to ASTM D1895-69.
［実施例１］
１．イオン交換性層状珪酸塩の化学処理
撹拌翼と還流装置を取り付けた２Ｌセパラブルフラスコに、純水９２９ｇを投入し、９６％硫酸１０４ｇを滴下した。内温が８０℃になるまでオイルバスで加熱し、目標温度に到達したところで、さらに、造粒モンモリロナイト（構造：水澤化学社製、ベンクレイＳＬ、平均粒径：１８μｍ、粒度分布＝７〜３０μｍ、組成（ｗｔ％）：Ａｌ＝８．８７、Ｓｉ＝３３．７、主金属原子＝Ａｌ）を１００ｇ添加後撹拌した。このとき、イオン強度は３．３０ｍｏｌ／Ｌであった。
その後８０℃を保ちながら６６０分反応させた。この反応溶液を０．５ｌの純水に空けることで反応を停止し、さらに、このスラリーをヌッチェと吸引瓶にアスピレータを接続した装置にて濾過し、その後１Ｌの純水で３回洗浄した。
回収したケーキは、１２０℃で終夜乾燥後、７０ｇ秤取り、次工程に用いた。この粘土は、１Ｌプラスチックビーカーにて硫酸リチウム水和物１０８ｇを純水４８０ｍｌに溶解した水溶液に加えて、室温で２時間反応させた。このスラリーをヌッチェと吸引瓶にアスピレータを接続した装置にて濾過し、０．７Ｌの純水で３回洗浄し、回収したケーキを１２０℃で終夜乾燥した。その結果、６９．３ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１７．２μｍの粒子を得た。組成（ｗｔ％）は、Ａｌが６．１０、Ｓｉが３８．９であり、Ａｌの溶出率は４４％であった。窒素吸着法により測定した平均細孔径は５．８ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１７ｍｌ／ｇであった。ＢＥＴ比表面積は２９０ｍ２／ｇであった。
[Example 1]
1. Chemical treatment of ion-exchange layered silicate Into a 2 L separable flask equipped with a stirring blade and a reflux device, 929 g of pure water was added, and 104 g of 96% sulfuric acid was added dropwise. Heated with an oil bath until the internal temperature reached 80 ° C., and when the target temperature was reached, granulated montmorillonite (structure: manufactured by Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 18 μm, particle size distribution = 7-30 μm, 100 g of composition (wt%): Al = 8.87, Si = 33.7, main metal atom = Al) was added and stirred. At this time, the ionic strength was 3.30 mol / L.
Thereafter, the mixture was reacted for 660 minutes while maintaining 80 ° C. The reaction was stopped by emptying the reaction solution in 0.5 l of pure water, and the slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and then washed with 1 L of pure water three times.
The recovered cake was dried at 120 ° C. overnight, then weighed 70 g and used in the next step. This clay was added to an aqueous solution in which 108 g of lithium sulfate hydrate was dissolved in 480 ml of pure water in a 1 L plastic beaker and reacted at room temperature for 2 hours. The slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, washed with 0.7 L of pure water three times, and the recovered cake was dried at 120 ° C. overnight. As a result, 69.3 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an aperture of 53 μm to obtain particles having an average particle diameter of 17.2 μm. The composition (wt%) was 6.10 for Al and 38.9 for Si, and the elution rate of Al was 44%. The average pore diameter measured by the nitrogen adsorption method was 5.8 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.17 ml / g. The BET specific surface area was 290 m 2 / g.
２．触媒調製
以下の操作は、不活性ガス下、脱酸素、脱水処理された溶媒、モノマーを使用して実施した。
化学処理したモンモリロナイト粒子を容積２００ｍｌのフラスコに入れ、２００℃でおよそ３時間（突沸がおさまってから２時間以上）減圧乾燥した。この乾燥モンモリロナイトの水分含量を測定したところ、水分値は０．９２ｗｔ％であった。内容積１Ｌのフラスコに上記乾燥モンモリロナイト２０．１ｇを秤量し、ヘプタン１４１ｍｌ、トリイソブチルアルミニウム（ＴｉＢＡ）のヘプタン溶液６９．０ｍｌ（４９．４ｍｍｏｌ、濃度１４１．９ｍｇ／ｌ）を加え、室温で１時間撹拌した。その後、ヘプタンで残液率１／１００まで洗浄し、最後にスラリー量を１００ｍｌに調製した。これに、ヘプタン１００ｍｌとＴｎＯＡのヘプタン溶液３．１ｍｌ（濃度１４３．６ｍｇ／ｍｌ、１２１４μｍｏｌ）を加えた。
ここに、別のフラスコ（容積２００ｍｌ）中で、（ｒ）−［１，１´−ジメチルシリレンビス｛２−メチル−４−（４−クロロフェニル）−４Ｈ−アズレニル｝］ハフニウムジクロライド（合成は、特開平１０−１１０１３６号公報の実施例に従って実施した。）２５４ｍｇ（３１２．４μｍｏｌ）にヘプタン（４８ｍＬ）を加えたスラリーを加えて、６０℃で６０分間撹拌した。ヘプタンを追加して３３３ｍｌに調製した。
窒素置換を行った内容積１Ｌの撹拌式オートクレーブに、上記調製したモンモリロナイト／メタロセン錯体導入した。オートクレーブ内の温度が４０℃に安定したところでプロピレンを１０ｇ／時間の速度で供給し、温度４０℃を維持した。４時間後プロピレンの供給を停止し、さらに１時間維持して予備重合を行った。
予備重合終了後、残存プロピレンをパージして予備重合触媒スラリーをオートクレーブより回収した。回収した予備重合触媒スラリーを静置し、上澄み液を２１５ｍｌ抜き出した。続いてＴｉＢＡのヘプタン溶液８．６ｍｌ（６．１ｍｍｏｌ）を室温にて加え、その後、４０℃にて１時間減圧乾燥した。これにより、触媒１ｇ当たりポリプロピレン２．１８ｇ含む予備重合触媒が６５．２ｇ得られた。
2. Catalyst preparation The following operations were carried out under inert gas using deoxygenated and dehydrated solvents and monomers.
Chemically treated montmorillonite particles were placed in a 200 ml volumetric flask and dried under reduced pressure at 200 ° C. for about 3 hours (2 hours or more after bumping had subsided). When the moisture content of this dried montmorillonite was measured, the moisture value was 0.92 wt%. 20.1 g of the dried montmorillonite was weighed into a 1 L flask, and 141 ml of heptane and 69.0 ml (49.4 mmol, concentration 141.9 mg / l) of heptane solution of triisobutylaluminum (TiBA) were added for 1 hour at room temperature. Stir. Thereafter, the residue was washed with heptane to a residual liquid ratio of 1/100, and finally the amount of slurry was adjusted to 100 ml. To this, 100 ml of heptane and 3.1 ml of a heptane solution of TnOA (concentration 143.6 mg / ml, 1214 μmol) were added.
In another flask (volume 200 ml), (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] hafnium dichloride (synthesis is It carried out according to the Example of Unexamined-Japanese-Patent No. 10-110136.) The slurry which added heptane (48 mL) to 254 mg (312.4 micromol) was added, and it stirred at 60 degreeC for 60 minutes. Heptane was added to prepare 333 ml.
The montmorillonite / metallocene complex prepared above was introduced into a stirring autoclave having an internal volume of 1 L subjected to nitrogen substitution. When the temperature in the autoclave was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature at 40 ° C. After 4 hours, the supply of propylene was stopped and maintained for another 1 hour for prepolymerization.
After the prepolymerization, the remaining propylene was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and 215 ml of the supernatant was extracted. Subsequently, 8.6 ml (6.1 mmol) of a heptane solution of TiBA was added at room temperature, and then dried under reduced pressure at 40 ° C. for 1 hour. As a result, 65.2 g of a prepolymerized catalyst containing 2.18 g of polypropylene per 1 g of catalyst was obtained.
３．プロピレンの重合
内容積３Ｌの攪拌式オートクレーブ内をプロピレンで十分置換した後に、ＴｉＢＡのヘプタン溶液２ｍｌ（２．０２ｍｍｏｌ）を加え、水素３０ｍｌ、液体プロピレン７５０ｍｌを導入し、７０℃に昇温しその温度を維持した。予備重合触媒をヘプタンでスラリー化し、触媒として（予備重合ポリマーの重量は除く）２０ｍｇを圧入し重合を開始した。内温を７０℃に維持したまま、１時間重合を継続した。その後、エタノール５ｍｌを加え重合反応を停止させた。残ガスをパージしてポリマーを得た。得られたポリマーを９０℃で１時間乾燥した。
その結果、２４０ｇのポリマーが得られた。触媒活性は、１２０００ｇ−ＰＰ／ｇ−触媒であった。ＭＦＲは１．１ｇ／１０分、ポリマーの嵩密度は０．４２ｇ／ｃｍ３であった。結果を表１に示す。
3. Polymerization of propylene After the inside of the stirred autoclave with an internal volume of 3 L was sufficiently substituted with propylene, 2 ml (2.02 mmol) of a heptane solution of TiBA was added, 30 ml of hydrogen and 750 ml of liquid propylene were introduced, and the temperature was raised to 70 ° C. Maintained. The prepolymerized catalyst was slurried with heptane, and 20 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. While maintaining the internal temperature at 70 ° C., polymerization was continued for 1 hour. Thereafter, 5 ml of ethanol was added to stop the polymerization reaction. The residual gas was purged to obtain a polymer. The resulting polymer was dried at 90 ° C. for 1 hour.
As a result, 240 g of polymer was obtained. The catalytic activity was 12000 g-PP / g-catalyst. The MFR was 1.1 g / 10 min and the bulk density of the polymer was 0.42 g / cm 3 . The results are shown in Table 1.
［実施例２］
１．イオン交換性層状珪酸塩の化学処理
酸処理時の温度を７５℃、反応時間を５８０分とする以外は、実施例１のイオン交換性層状珪酸塩の化学処理と同様に行った。その結果、７２．５ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１８．２μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は３９％であった。窒素吸着法により測定した平均細孔径は５．７ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１６ｍｌ／ｇであった。ＢＥＴ比表面積は２９０ｍ２／ｇであった。
[Example 2]
1. Chemical treatment of ion-exchange layered silicate The same treatment as in Example 1 was conducted except that the temperature during acid treatment was 75 ° C. and the reaction time was 580 minutes. As a result, 72.5 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 18.2 μm. As a result of the composition analysis, the elution rate of Al was 39%. The average pore diameter measured by the nitrogen adsorption method was 5.7 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.16 ml / g. The BET specific surface area was 290 m 2 / g.
２．触媒の調製およびプロピレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．１２ｇを含む予備重合触媒を６４．８ｇ得た。これを用いて、実施例１記載と同様にして、プロピレンの重合を行った。その結果、触媒活性は、１１０００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．５ｇ／１０分、ポリマーの嵩密度は０．４３ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 64.8 g of a prepolymerized catalyst containing 2.12 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene was polymerized in the same manner as described in Example 1. As a result, the catalytic activity was 11000 g-PP / g-catalyst, MFR was 1.5 g / 10 min, and the bulk density of the polymer was 0.43 g / cm 3 . The results are shown in Table 1.
［実施例３］
１．イオン交換性層状珪酸塩の化学処理
反応温度を８５℃、反応時間を４８０分とする以外は、実施例１のイオン交換性層状珪酸塩の化学処理と同様に行った。その結果、７３．９ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１７．８μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は３８％であった。窒素吸着法により測定した平均細孔径は５．５ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１５ｍｌ／ｇであった。ＢＥＴ比表面積は３１１ｍ２／ｇであった。
[Example 3]
1. Chemical treatment of ion-exchange layered silicate The same treatment as in Example 1 was performed except that the reaction temperature was 85 ° C. and the reaction time was 480 minutes. As a result, 73.9 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 17.8 μm. As a result of the composition analysis, the elution rate of Al was 38%. The average pore diameter measured by the nitrogen adsorption method was 5.5 nm, and the micropore volume within the pore diameter range of 2 to 6 nm was 0.15 ml / g. The BET specific surface area was 311 m 2 / g.
２．触媒の調製およびプロピレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．１８ｇを含む予備重合触媒を６５．２ｇ得た。これを用いて、実施例１記載と同様にして、プロピレンの重合を行った。その結果、触媒活性は、１０５００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．２ｇ／１０分、ポリマーの嵩密度は０．４５ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 65.2 g of a prepolymerized catalyst containing 2.18 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene was polymerized in the same manner as described in Example 1. As a result, the catalytic activity was 10500 g-PP / g-catalyst, the MFR was 1.2 g / 10 min, and the bulk density of the polymer was 0.45 g / cm 3 . The results are shown in Table 1.
［実施例４］
１．イオン交換性層状珪酸塩の化学処理
酸処理時の温度を１００℃、蒸留水を６９４ｇ，硫酸を８４ｇ，反応時間を２４０分とする以外は、実施例１のイオン交換性層状珪酸塩の化学処理と同様に行った。イオン強度は３．８０ｍｏｌ／Ｌであった。その結果、７０．３ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１７．３μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は３５％であった。窒素吸着法により測定した平均細孔径は５．０ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１６ｍｌ／ｇであった。ＢＥＴ比表面積は３１３ｍ２／ｇであった。
[Example 4]
1. Chemical treatment of ion-exchange layered silicate Chemical treatment of ion-exchange layered silicate of Example 1 except that the temperature during acid treatment is 100 ° C., 694 g of distilled water, 84 g of sulfuric acid, and the reaction time is 240 minutes. As well as. The ionic strength was 3.80 mol / L. As a result, 70.3 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an aperture of 53 μm to obtain particles having an average particle diameter of 17.3 μm. As a result of the composition analysis, the elution rate of Al was 35%. The average pore diameter measured by the nitrogen adsorption method was 5.0 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.16 ml / g. The BET specific surface area was 313 m 2 / g.
２．触媒の調製およびプロピレンとエチレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に、触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．１２ｇを含む予備重合触媒を６４．８ｇ得た。これを用いて、水素を重合槽に添加する前にエチレンを１６．５ｇ添加し、水素を４５ｍｌ、触媒を１５ｍｇ用いた以外は、実施例１記載と同様にして、プロピレンとエチレンの重合を行った。
その結果、触媒活性は、１９８００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは０．３７ｇ／１０分、ポリマーの嵩密度は０．４６ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene and ethylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 64.8 g of a prepolymerized catalyst containing 2.12 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 1, except that 16.5 g of ethylene was added before adding hydrogen to the polymerization tank, 45 ml of hydrogen and 15 mg of catalyst were used. It was.
As a result, the catalyst activity was 19800 g-PP / g-catalyst, MFR was 0.37 g / 10 min, and the bulk density of the polymer was 0.46 g / cm 3 . The results are shown in Table 1.
［実施例５］
１．イオン交換性層状珪酸塩の化学処理
酸処理時の温度を９５℃，反応時間を３８０分とする以外は、実施例４のイオン交換性層状珪酸塩の化学処理と同様に行った。イオン強度は３．８０ｍｏｌ／Ｌであった。その結果、６９．１ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１７．０μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は３９％であった。窒素吸着法により測定した平均細孔径は５．２ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１６ｍｌ／ｇであった。ＢＥＴ比表面積は３１８ｍ２／ｇであった。
[Example 5]
1. Chemical treatment of ion-exchange layered silicate The same treatment as that of the ion-exchange layered silicate in Example 4 was conducted except that the temperature during acid treatment was 95 ° C. and the reaction time was 380 minutes. The ionic strength was 3.80 mol / L. As a result, 69.1 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 17.0 μm. As a result of the composition analysis, the elution rate of Al was 39%. The average pore diameter measured by the nitrogen adsorption method was 5.2 nm, and the micropore volume within the pore diameter range of 2 to 6 nm was 0.16 ml / g. The BET specific surface area was 318 m 2 / g.
２．触媒の調製およびプロピレンとエチレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．１３ｇを含む予備重合触媒を６５．１ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、１９７００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは０．４４ｇ／１０分、ポリマーの嵩密度は０．４６ｇ／ｃｍ３であった。結果を表１に示す。
2. Catalyst Preparation and Polymerization of Propylene and Ethylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 65.1 g of a prepolymerized catalyst containing 2.13 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalyst activity was 19700 g-PP / g-catalyst, the MFR was 0.44 g / 10 min, and the bulk density of the polymer was 0.46 g / cm 3 . The results are shown in Table 1.
［実施例６］
１．イオン交換性層状珪酸塩の化学処理
酸処理時の温度を９０℃、蒸留水を６１０ｇ，硫酸を１２５ｇ，反応時間を３３０分とする以外は、実施例１のイオン交換性層状珪酸塩の化学処理と同様に行った。イオン強度は６．０２ｍｏｌ／Ｌであった。その結果、６１．８ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１８．２μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は４１％であった。窒素吸着法により測定した平均細孔径は５．８ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１４ｍｌ／ｇであった。ＢＥＴ比表面積は２９０ｍ２／ｇであった。
[Example 6]
1. Chemical treatment of ion-exchange layered silicate Chemical treatment of ion-exchange layered silicate of Example 1 except that the temperature during acid treatment is 90 ° C., distilled water is 610 g, sulfuric acid is 125 g, and reaction time is 330 minutes. As well as. The ionic strength was 6.02 mol / L. As a result, 61.8 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 18.2 μm. As a result of the composition analysis, the elution rate of Al was 41%. The average pore diameter measured by the nitrogen adsorption method was 5.8 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.14 ml / g. The BET specific surface area was 290 m 2 / g.
２．触媒の調製およびププロピレンとエチレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に、触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．１５ｇを含む予備重合触媒を６５．３ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、１９５００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは０．４１ｇ／１０分、ポリマーの嵩密度は０．４６ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene and ethylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 65.3 g of a prepolymerized catalyst containing 2.15 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalytic activity was 19500 g-PP / g-catalyst, the MFR was 0.41 g / 10 min, and the bulk density of the polymer was 0.46 g / cm 3 . The results are shown in Table 1.
［実施例７］
１．イオン交換性層状珪酸塩の化学処理
酸処理時の温度を９０℃、蒸留水を１５８ｇ、硫酸を２５ｇ、モンモリロナイトを２５ｇ、反応時間を３００分とする以外は、実施例１のイオン交換性層状珪酸塩の化学処理と同様に行った。イオン強度は４．６５ｍｏｌ／Ｌであった。その結果、１６．５ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１８．２μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は３２％であった。窒素吸着法により測定した平均細孔径は５．０ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１５ｍｌ／ｇであった。ＢＥＴ比表面積は３０１ｍ２／ｇであった。
[Example 7]
1. Chemical treatment of ion-exchange layered silicate The ion-exchange layered silicate of Example 1 except that the temperature during the acid treatment is 90 ° C., distilled water is 158 g, sulfuric acid is 25 g, montmorillonite is 25 g, and the reaction time is 300 minutes. Similar to the chemical treatment of the salt. The ionic strength was 4.65 mol / L. As a result, 16.5 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 18.2 μm. As a result of the composition analysis, the elution rate of Al was 32%. The average pore diameter measured by the nitrogen adsorption method was 5.0 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.15 ml / g. The BET specific surface area was 301 m 2 / g.
２．触媒の調製およびププロピレンとエチレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に、触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．１３ｇを含む予備重合触媒を６５．３ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、２１６００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは０．４５ｇ／１０分、ポリマーの嵩密度は０．４５ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene and ethylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 65.3 g of a prepolymerized catalyst containing 2.13 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalytic activity was 21600 g-PP / g-catalyst, the MFR was 0.45 g / 10 min, and the bulk density of the polymer was 0.45 g / cm 3 . The results are shown in Table 1.
［実施例８］
１．イオン交換性層状珪酸塩の化学処理
酸処理時の温度を９０℃、蒸留水を４６１ｇ、硫酸を４１．３ｇ、反応時間を１２００分とする以外は、実施例１のイオン交換性層状珪酸塩の化学処理と同様に行った。イオン強度は２．６６ｍｏｌ／Ｌであった。その結果、６２．５ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１７．４μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は４０％であった。窒素吸着法により測定した平均細孔径は５．４ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１８ｍｌ／ｇであった。ＢＥＴ比表面積は３３５ｍ２／ｇであった。
[Example 8]
1. Chemical treatment of ion-exchange layered silicate The ion-exchange layered silicate of Example 1 was used except that the temperature during acid treatment was 90 ° C, distilled water was 461 g, sulfuric acid was 41.3 g, and the reaction time was 1200 minutes. Similar to chemical treatment. The ionic strength was 2.66 mol / L. As a result, 62.5 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an aperture of 53 μm to obtain particles having an average particle diameter of 17.4 μm. As a result of the composition analysis, the elution rate of Al was 40%. The average pore diameter measured by the nitrogen adsorption method was 5.4 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.18 ml / g. The BET specific surface area was 335 m 2 / g.
２．触媒の調製およびプロピレンとエチレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．１９ｇを含む予備重合触媒を６５．４ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、２０９００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは０．５６ｇ／１０分、ポリマーの嵩密度は０．４５ｇ／ｃｍ３であった。結果を表１に示す。
2. Catalyst Preparation and Polymerization of Propylene and Ethylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 65.4 g of a prepolymerized catalyst containing 2.19 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalytic activity was 20900 g-PP / g-catalyst, the MFR was 0.56 g / 10 min, and the bulk density of the polymer was 0.45 g / cm 3 . The results are shown in Table 1.
［実施例９］
１．イオン交換性層状珪酸塩の化学処理
酸処理時の温度を９０℃、蒸留水を６８７ｇ、硫酸を４１．４ｇ、モンモリロナイトを５１ｇ、反応時間を１４４０分とする以外は、実施例１のイオン交換性層状珪酸塩の化学処理と同様に行った。イオン強度は１．７６ｍｏｌ／Ｌであった。その結果、６６．３ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１８．０μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は３６％であった。窒素吸着法により測定した平均細孔径は５．３ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１６ｍｌ／ｇであった。ＢＥＴ比表面積は３０５ｍ２／ｇであった。
[Example 9]
1. Chemical treatment of ion-exchange layered silicate The ion-exchange property of Example 1 except that the temperature during acid treatment is 90 ° C., distilled water is 687 g, sulfuric acid is 41.4 g, montmorillonite is 51 g, and the reaction time is 1440 minutes. It carried out like the chemical treatment of layered silicate. The ionic strength was 1.76 mol / L. As a result, 66.3 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 18.0 μm. As a result of the composition analysis, the elution rate of Al was 36%. The average pore diameter measured by the nitrogen adsorption method was 5.3 nm, and the micropore volume within the pore diameter range of 2 to 6 nm was 0.16 ml / g. The BET specific surface area was 305 m 2 / g.
２．触媒の調製およびプロピレンとエチレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．２０ｇを含む予備重合触媒を６５．１ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、１８０００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．５０ｇ／１０分、ポリマーの嵩密度は０．４５ｇ／ｃｍ３であった。結果を表１に示す。
2. Catalyst Preparation and Polymerization of Propylene and Ethylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 65.1 g of a prepolymerized catalyst containing 2.20 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalyst activity was 18000 g-PP / g-catalyst, MFR was 1.50 g / 10 min, and the bulk density of the polymer was 0.45 g / cm 3 . The results are shown in Table 1.
［実施例１０］
１．イオン交換性層状珪酸塩の化学処理
酸処理時の温度を８５℃，反応時間を６６０分とする以外は、実施例４のイオン交換性層状珪酸塩の化学処理と同様に行った。イオン強度は３．８０ｍｏｌ／Ｌであった。その結果、５８．８ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１８．０μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は４１％であった。窒素吸着法により測定した平均細孔径は５．３ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１８ｍｌ／ｇであった。ＢＥＴ比表面積は３２４ｍ２／ｇであった。
[Example 10]
1. Chemical treatment of ion-exchange layered silicate The same treatment as that of the ion-exchange layered silicate of Example 4 was performed except that the temperature during acid treatment was 85 ° C. and the reaction time was 660 minutes. The ionic strength was 3.80 mol / L. As a result, 58.8 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 18.0 μm. As a result of the composition analysis, the elution rate of Al was 41%. The average pore diameter measured by the nitrogen adsorption method was 5.3 nm, and the micropore volume within the pore diameter range of 2 to 6 nm was 0.18 ml / g. The BET specific surface area was 324 m 2 / g.
２．触媒の調製およびプロピレンとエチレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．１８ｇを含む予備重合触媒を６５．１ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、２１０００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは０．５６ｇ／１０分、ポリマーの嵩密度は０．４５ｇ／ｃｍ３であった。結果を表１に示す。
2. Catalyst Preparation and Polymerization of Propylene and Ethylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 65.1 g of a prepolymerized catalyst containing 2.18 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalyst activity was 21000 g-PP / g-catalyst, MFR was 0.56 g / 10 min, and the bulk density of the polymer was 0.45 g / cm 3 . The results are shown in Table 1.
［実施例１１］
１．触媒の調製およびプロピレンとエチレンの重合
（ｒ）−［１，１´−ジメチルシリレンビス｛２−メチル−４−（４−クロロフェニル）−４Ｈ−アズレニル｝］ハフニウムジクロライドの代わりに、（ｒ）−［１，１´−ジメチルシリレンビス｛２−メチル−４−（４−クロロフェニル）−４Ｈ−アズレニル｝］ジルコニウムクロライド（合成は、特開平１０−１１０１３６号公報の実施例に従って実施した。）２２０ｍｇ（３０３．４μｍｏｌ）を使用する以外は、実施例１の化学処理モンモリロナイトを使用し、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．０９ｇを含む予備重合触媒を６２．９１ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、１５０００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは０．９ｇ／１０分、ポリマーの嵩密度は０．４８ｇ／ｃｍ３であった。結果を表１に示す。
[Example 11]
1. Preparation of catalyst and polymerization of propylene and ethylene (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] hafnium dichloride instead of (r)- 220 mg of [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium chloride (synthesized according to the example of JP-A-10-110136). The catalyst was prepared in the same manner as in Example 1 except that the chemically treated montmorillonite of Example 1 was used except that 303.4 μmol) was used.
As a result, 62.91 g of a prepolymerized catalyst containing 2.09 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalytic activity was 15000 g-PP / g-catalyst, the MFR was 0.9 g / 10 min, and the bulk density of the polymer was 0.48 g / cm 3 . The results are shown in Table 1.
［比較例１］
１．イオン交換性層状珪酸塩の化学処理
撹拌翼と還流装置を取り付けた３Ｌセパラブルフラスコに、純水２２６４ｇを投入し、９６％硫酸６７０ｇを滴下した。内温が９０℃になるまでオイルバスで加熱し、目標温度に到達したところで、さらに造粒モンモリロナイト（構造：水澤化学社製、ベンクレイＳＬ、平均粒径：１８μｍ、粒度分布＝７〜３０μｍ、組成（ｗｔ％）：Ａｌ＝９．１１、Ｓｉ＝３２．９、主金属原子＝Ａｌ）を４００ｇ添加後撹拌した。このとき、酸濃度は１９．７ｗｔ％で、粘土に対する酸濃度は１６．４ｍｍｏｌ／ｇであった。また、イオン強度は８．８７ｍｏｌ／Ｌであった。その後、９０℃を保ちながら２４０分反応させた。この反応溶液を２Ｌの純水に空けることで反応を停止し、さらに、このスラリーをヌッチェと吸引瓶にアスピレータを接続した装置にて濾過し、その後４Ｌの純水で３回洗浄した。
回収したケーキは、１２０℃で終夜乾燥後、１００ｇ秤取り次工程に用いた。１Ｌプラスチックビーカーにて硫酸リチウム水和物１０８ｇを純水４８１ｍｌに溶解した水溶液に回収したケーキを加えて室温で２時間反応させた。このスラリーをヌッチェと吸引瓶にアスピレータを接続した装置にて濾過し、３Ｌの純水で３回洗浄した。
回収したケーキを１２０℃で終夜乾燥した。その結果、７３．３ｇの化学処理モンモリロナイトを得た。これを目開き５３μｍの篩にて篩い分けし、平均粒径１７．１μｍの粒子を７２．３ｇ得た。
化学処理モンモリロナイトの組成（ｗｔ％）は、Ａｌが６．５２、Ｓｉが３８．２含まれており、ＡｌとＳｉのモル比は０．１７８であり、Ａｌの溶出率は３９％であった。窒素吸着法により測定した平均細孔径は５．９ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１３ｍｌ／ｇであった。ＢＥＴ比表面積は２６０ｍ２／ｇであった。
[Comparative Example 1]
1. Chemical treatment of ion-exchange layered silicate Into a 3 L separable flask equipped with a stirring blade and a reflux apparatus, 2264 g of pure water was added and 670 g of 96% sulfuric acid was added dropwise. Heated in an oil bath until the internal temperature reached 90 ° C., and when the target temperature was reached, further granulated montmorillonite (structure: manufactured by Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 18 μm, particle size distribution = 7-30 μm, composition (Wt%): Al = 9.11, Si = 32.9, main metal atom = Al) was added and stirred after adding 400 g. At this time, the acid concentration was 19.7 wt%, and the acid concentration relative to the clay was 16.4 mmol / g. The ionic strength was 8.87 mol / L. Then, it was made to react for 240 minutes, keeping 90 degreeC. The reaction was stopped by emptying the reaction solution in 2 L of pure water, and the slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and then washed with 4 L of pure water three times.
The recovered cake was dried at 120 ° C. overnight and then weighed 100 g and used in the next step. The recovered cake was added to an aqueous solution in which 108 g of lithium sulfate hydrate was dissolved in 481 ml of pure water in a 1 L plastic beaker, and reacted at room temperature for 2 hours. This slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, and washed three times with 3 L of pure water.
The collected cake was dried at 120 ° C. overnight. As a result, 73.3 g of chemically treated montmorillonite was obtained. This was sieved with a sieve having an aperture of 53 μm to obtain 72.3 g of particles having an average particle diameter of 17.1 μm.
The composition (wt%) of the chemically treated montmorillonite contained 6.52 Al and 38.2 Si, the molar ratio of Al to Si was 0.178, and the elution rate of Al was 39%. . The average pore diameter measured by the nitrogen adsorption method was 5.9 nm, and the micropore volume within the pore diameter range of 2 to 6 nm was 0.13 ml / g. The BET specific surface area was 260 m 2 / g.
２．触媒の調製およびプロピレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．１６ｇを含む予備重合触媒を６３．１ｇ得た。これを用いて、実施例１記載と同様にして、プロピレンの重合を行った。その結果、触媒活性は、８０００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．５ｇ／１０分、ポリマーの嵩密度は０．４３ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 63.1 g of a prepolymerized catalyst containing 2.16 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene was polymerized in the same manner as described in Example 1. As a result, the catalytic activity was 8000 g-PP / g-catalyst, the MFR was 1.5 g / 10 min, and the bulk density of the polymer was 0.43 g / cm 3 . The results are shown in Table 1.
［比較例２］
１．イオン交換性層状珪酸塩の化学処理
酸処理時の反応時間を４８０分とする以外は、比較例１のイオン交換性層状珪酸塩の化学処理と同様に行った。その結果、４３．８ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１７．２μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は６３％であった。窒素吸着法により測定した平均細孔径は７．１ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１２ｍｌ／ｇであった。ＢＥＴ比表面積は２５５ｍ２／ｇであった。
[Comparative Example 2]
1. Chemical treatment of ion-exchange layered silicate The same treatment as the chemical treatment of ion-exchange layered silicate of Comparative Example 1 was conducted except that the reaction time during the acid treatment was 480 minutes. As a result, 43.8 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an aperture of 53 μm to obtain particles having an average particle diameter of 17.2 μm. As a result of the composition analysis, the elution rate of Al was 63%. The average pore diameter measured by the nitrogen adsorption method was 7.1 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.12 ml / g. The BET specific surface area was 255 m 2 / g.
２．触媒の調製およびプロピレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．２０ｇを含む予備重合触媒を６３．８ｇ得た。これを用いて、実施例１記載と同様にして、プロピレンの重合を行った。その結果、触媒活性は、６５００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．７ｇ／１０分、ポリマーの嵩密度は０．４２ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 63.8 g of a prepolymerized catalyst containing 2.20 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene was polymerized in the same manner as described in Example 1. As a result, the catalytic activity was 6500 g-PP / g-catalyst, MFR was 1.7 g / 10 min, and the bulk density of the polymer was 0.42 g / cm 3 . The results are shown in Table 1.
［比較例３］
純水を４５．６ｇ、酸濃度を４０．０％とし、反応時間を３００分とする以外は、実施例１と同様にして、イオン交換性層状珪酸塩の化学処理を行った。イオン強度は２５．１２ｍｏｌ／Ｌであった。その結果、５１．０ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１７．８μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は５２％であった。窒素吸着法により測定した平均細孔径は８．４ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．０８ｍｌ／ｇであった。ＢＥＴ比表面積は２１４ｍ２／ｇであった。
[Comparative Example 3]
The ion-exchange layered silicate was chemically treated in the same manner as in Example 1 except that 45.6 g of pure water, acid concentration of 40.0%, and reaction time of 300 minutes were used. The ionic strength was 25.12 mol / L. As a result, 51.0 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 17.8 μm. As a result of the composition analysis, the elution rate of Al was 52%. The average pore diameter measured by the nitrogen adsorption method was 8.4 nm, and the micropore volume within the pore diameter range of 2 to 6 nm was 0.08 ml / g. The BET specific surface area was 214 m 2 / g.
２．触媒の調製およびプロピレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン１．９８ｇを含む予備重合触媒を５９．６ｇ得た。これを用いて、実施例１記載と同様にして、プロピレンの重合を行った。その結果、触媒活性は、５２００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは２．０ｇ／１０分、ポリマーの嵩密度は０．４３ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 59.6 g of a prepolymerized catalyst containing 1.98 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene was polymerized in the same manner as described in Example 1. As a result, the catalytic activity was 5200 g-PP / g-catalyst, MFR was 2.0 g / 10 min, and the bulk density of the polymer was 0.43 g / cm 3 . The results are shown in Table 1.
［比較例４］
酸処理の反応を還流条件で、反応時間を１２０分で行う以外は、比較例１と同様にしてイオン交換性層状珪酸塩の化学処理を行った。その結果、７２．５ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１８．８μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は３７％であった。窒素吸着法により測定した平均細孔径は６．８ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１３ｍｌ／ｇであった。ＢＥＴ比表面積は２４０ｍ２／ｇであった。
[Comparative Example 4]
The ion-exchanged layered silicate was chemically treated in the same manner as in Comparative Example 1 except that the acid treatment reaction was performed under reflux conditions and the reaction time was 120 minutes. As a result, 72.5 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 18.8 μm. As a result of the composition analysis, the elution rate of Al was 37%. The average pore diameter measured by the nitrogen adsorption method was 6.8 nm, and the micropore volume within the pore diameter range of 2 to 6 nm was 0.13 ml / g. The BET specific surface area was 240 m 2 / g.
２．触媒の調製およびプロピレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．０８ｇを含む予備重合触媒を６１．６ｇ得た。これを用いて、実施例１記載と同様にして、プロピレンの重合を行った。その結果、触媒活性は、８２００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．５ｇ／１０分、ポリマーの嵩密度は０．４２ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 61.6 g of a prepolymerized catalyst containing 2.08 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene was polymerized in the same manner as described in Example 1. As a result, the catalytic activity was 8200 g-PP / g-catalyst, the MFR was 1.5 g / 10 min, and the bulk density of the polymer was 0.42 g / cm 3 . The results are shown in Table 1.
［比較例５］
酸処理の反応温度を８０℃、反応時間を４５０分で行う以外は、比較例１と同様にしてイオン交換性層状珪酸塩の化学処理を行った。その結果、６８．８ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１８．５μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は３７％であった。窒素吸着法により測定した平均細孔径は６．０ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１３ｍｌ／ｇであった。ＢＥＴ比表面積は２５２ｍ２／ｇであった。
[Comparative Example 5]
The chemical treatment of the ion-exchange layered silicate was performed in the same manner as in Comparative Example 1 except that the reaction temperature of the acid treatment was 80 ° C. and the reaction time was 450 minutes. As a result, 68.8 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 18.5 μm. As a result of the composition analysis, the elution rate of Al was 37%. The average pore diameter measured by the nitrogen adsorption method was 6.0 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.13 ml / g. The BET specific surface area was 252 m 2 / g.
２．触媒の調製およびプロピレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．２０ｇを含む予備重合触媒を６３．７ｇ得た。これを用いて、実施例１記載と同様にして、プロピレンの重合を行った。その結果、触媒活性は、７５００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．７ｇ／１０分、ポリマーの嵩密度は０．４２ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 63.7 g of a prepolymerized catalyst containing 2.20 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene was polymerized in the same manner as described in Example 1. As a result, the catalytic activity was 7500 g-PP / g-catalyst, MFR was 1.7 g / 10 min, and the bulk density of the polymer was 0.42 g / cm 3 . The results are shown in Table 1.
［比較例６］
蒸留水を２３１．３ｇ、硫酸を４９６．７ｇとし、反応時間を２４０分とする以外は、実施例１と同等してイオン交換性層状珪酸塩の化学処理を行った。イオン強度は６３．３４ｍｏｌ／Ｌであった。その結果、５７．５ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１７．５μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は４４％であった。窒素吸着法により測定した平均細孔径は６．９ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１１ｍｌ／ｇであった。ＢＥＴ比表面積は２１４ｍ２／ｇであった。
[Comparative Example 6]
A chemical treatment of the ion-exchange layered silicate was performed in the same manner as in Example 1 except that 231.3 g of distilled water and 496.7 g of sulfuric acid were used and the reaction time was 240 minutes. The ionic strength was 63.34 mol / L. As a result, 57.5 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 17.5 μm. As a result of the composition analysis, the elution rate of Al was 44%. The average pore diameter measured by the nitrogen adsorption method was 6.9 nm, and the micropore volume within the pore diameter range of 2 to 6 nm was 0.11 ml / g. The BET specific surface area was 214 m 2 / g.
２．触媒の調製およびプロピレンとエチレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．２０ｇを含む予備重合触媒を６３．７ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、３２００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．８ｇ／１０分、ポリマーの嵩密度は０．４５ｇ／ｃｍ３であった。結果を表１に示す。
2. Catalyst Preparation and Polymerization of Propylene and Ethylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 63.7 g of a prepolymerized catalyst containing 2.20 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalytic activity was 3200 g-PP / g-catalyst, MFR was 1.8 g / 10 min, and the bulk density of the polymer was 0.45 g / cm 3 . The results are shown in Table 1.
［比較例７］
蒸留水を４８３．３ｇ、硫酸を２９４．３ｇとし、反応時間を１８０分で行う以外は、比較例１と同様にしてイオン交換性層状珪酸塩の化学処理を行った。イオン強度は、１５．１６ｍｏｌ／Ｌであった。その結果、７２．３ｇの化学処理モンモリロナイトを得た。
これを目開き５３μｍの篩にて篩い分けし、平均粒径が１８．０μｍの粒子を得た。組成分析の結果、Ａｌの溶出率は３７％であった。窒素吸着法により測定した平均細孔径は６．４ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．０９ｍｌ／ｇであった。ＢＥＴ比表面積は２３６ｍ２／ｇであった。
[Comparative Example 7]
Chemical treatment of the ion-exchange layered silicate was carried out in the same manner as in Comparative Example 1, except that 483.3 g of distilled water and 294.3 g of sulfuric acid were used and the reaction time was 180 minutes. The ionic strength was 15.16 mol / L. As a result, 72.3 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 53 μm to obtain particles having an average particle diameter of 18.0 μm. As a result of the composition analysis, the elution rate of Al was 37%. The average pore diameter measured by the nitrogen adsorption method was 6.4 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.09 ml / g. The BET specific surface area was 236 m 2 / g.
２．触媒の調製およびプロピレンとエチレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．２１ｇを含む予備重合触媒を６３．５ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、４０００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．８ｇ／１０分、ポリマーの嵩密度は０．４５ｇ／ｃｍ３であった。結果を表１に示す。
2. Catalyst Preparation and Polymerization of Propylene and Ethylene A catalyst was prepared in the same manner as described in Example 1 except that the chemically treated montmorillonite described above was used.
As a result, 63.5 g of a prepolymerized catalyst containing 2.21 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalytic activity was 4000 g-PP / g-catalyst, the MFR was 1.8 g / 10 min, and the bulk density of the polymer was 0.45 g / cm 3 . The results are shown in Table 1.
［比較例８］
１．イオン交換性層状珪酸塩の化学処理
３５％塩酸３０ｇを脱塩水７０ｍｌに希釈し、次いで、市販のモンモリロナイト（クニピアＦ、主金属原子＝Ａｌ）１１．７ｇを分散させ、攪拌しながら昇温し２時間沸点処理を行った。このときの酸濃度は９．４ｗｔ％，イオン強度は３．２２ｍｏｌ／Ｌであった。その後、脱塩水で十分洗浄し、予備乾燥した後、２００℃減圧下で２時間乾燥させて化学処理モンモリロナイトを得た。
組成分析の結果、Ａｌの溶出率は４１％であった。窒素吸着法により測定した平均細孔径は６．５ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．０５ｍｌ／ｇであった。ＢＥＴ比表面積は２３０ｍ２／ｇであった。
[Comparative Example 8]
1. Chemical treatment of ion-exchange layered silicate 30 g of 35% hydrochloric acid is diluted in 70 ml of demineralized water, and then 11.7 g of commercially available montmorillonite (Kunipia F, main metal atom = Al) is dispersed, and the temperature is increased while stirring. Time boiling treatment was performed. At this time, the acid concentration was 9.4 wt%, and the ionic strength was 3.22 mol / L. Then, after sufficiently washing with demineralized water and pre-drying, it was dried under reduced pressure at 200 ° C. for 2 hours to obtain chemically treated montmorillonite.
As a result of the composition analysis, the elution rate of Al was 41%. The average pore diameter measured by the nitrogen adsorption method was 6.5 nm, and the micropore volume within the pore diameter range of 2 to 6 nm was 0.05 ml / g. The BET specific surface area was 230 m 2 / g.
２．触媒の調製およびプロピレンとエチレンの重合
１００ｍｌのフラスコに上記で得た化学処理モンモリロナイト３ｇを採取し、トルエン２０ｍｌに分散させてスラリーとし、室温にて撹拌下でトリエチルアルミニウム１３ｍｌを添加した。室温で１時間撹拌した後、デカンテーションによって上澄み液を除去し、固体部をトルエンで洗浄し、固体触媒成分を得た。
上記固体触媒成分１００ｍｇを秤量し、トリエチルアルミ０．５ｍｍｏｌ（Ａｌ原子換算）を加えた。ここに，実施例９で用いた（ｒ）−ジメチルシリレンビス｛１，１´−（２−メチル−４−フェニル−４−ヒドロアズレニル）｝ジルコニウムジクロライド０．９７５ｍｇ（１．５μｍｏｌ）をトルエン３ｍｌに希釈して導入した。
これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、５０００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．５ｇ／１０分、ポリマーの嵩密度は０．２８ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene and ethylene 3 g of the chemically treated montmorillonite obtained above was collected in a 100 ml flask, dispersed in 20 ml of toluene to form a slurry, and 13 ml of triethylaluminum was added with stirring at room temperature. After stirring at room temperature for 1 hour, the supernatant was removed by decantation, and the solid part was washed with toluene to obtain a solid catalyst component.
100 mg of the solid catalyst component was weighed, and 0.5 mmol of triethylaluminum (in terms of Al atom) was added. Here, 0.975 mg (1.5 μmol) of (r) -dimethylsilylenebis {1,1 ′-(2-methyl-4-phenyl-4-hydroazurenyl)} zirconium dichloride used in Example 9 was added to 3 ml of toluene. Dilute and introduce.
Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalytic activity was 5000 g-PP / g-catalyst, the MFR was 1.5 g / 10 min, and the bulk density of the polymer was 0.28 g / cm 3 . The results are shown in Table 1.
［比較例９］
１．触媒の調製およびプロピレンとエチレンの重合
（ｒ）−［１，１´−ジメチルシリレンビス｛２−メチル−４−（４−クロロフェニル）−４Ｈ−アズレニル｝］ハフニウムジクロライドの代わりに、実施例１０で用いた（ｒ）−［１，１´−ジメチルシリレンビス｛２−メチル−４−（４−クロロフェニル）−４Ｈ−アズレニル｝］ジルコニウムクロライド２１７ｍｇ（２９９．３μｍｏｌ）を使用する以外は、比較例１の化学処理モンモリロナイトを使用し、実施例１記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン２．１２ｇを含む予備重合触媒を６３．５ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、１３１００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．１ｇ／１０分、ポリマーの嵩密度は０．４７ｇ／ｃｍ３であった。結果を表１に示す。
[Comparative Example 9]
1. Preparation of catalyst and polymerization of propylene and ethylene (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium dichloride in Example 10 instead of Comparative Example 1 except that 217 mg (299.3 μmol) of (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium chloride used was used. Using the chemically treated montmorillonite, a catalyst was prepared in the same manner as described in Example 1.
As a result, 63.5 g of a prepolymerized catalyst containing 2.12 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalyst activity was 13100 g-PP / g-catalyst, MFR was 1.1 g / 10 min, and the bulk density of the polymer was 0.47 g / cm 3 . The results are shown in Table 1.
［比較例１０］
１．イオン交換性層状珪酸塩の化学処理
３リットルの撹拌翼の付いたガラス製セパラブルフラスコを使用し、蒸留水１５９０ミリリットル、硫酸マグネシウム７水和物３１８ｇ、続いて濃硫酸（９６％）２６１ｇをゆっくりと添加し、さらにモンモリロナイト（水澤化学社製ベンクレイＳＬ；平均粒径２５μｍ、粒度分布１０〜６０μｍ，組成（重量％）：Ａｌ８．４５、Ｍｇ２．１４、Ｆｅ２．３４、Ｓｉ３２．８、Ｎａ２．６２、主金属原子＝Ａｌ）を２４０ｇ分散させ、１０１℃℃まで１時間かけ昇温し、２時間その温度を維持した後、１時間で５０℃まで冷却した。イオン強度は８．５５ｍｌ／Ｌであった。このスラリーを減圧ろ過し、ケーキを回収した。さらに、このケーキを蒸留水で最終洗浄液のｐＨが３．５を越えるまで洗浄し、窒素雰囲気下１１０℃で終夜乾燥し，２０１．２ｇの化学処理モンモリロナイトを得た。
これを目開き７５μｍの篩にて篩い分けし、平均粒径が２４．７μｍの粒子を得た。
組成分析の結果、Ａｌの溶出率は２２％であった。窒素吸着法により測定した平均細孔径は４．８ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．３３ｍｌ／ｇであった。ＢＥＴ比表面積は２７５ｍ２／ｇであった。
[Comparative Example 10]
1. Chemical treatment of ion-exchange layered silicate Using a glass separable flask with a 3 liter stirring blade, slowly add 1590 ml of distilled water, 318 g of magnesium sulfate heptahydrate, followed by 261 g of concentrated sulfuric acid (96%). Montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL; average particle size 25 μm, particle size distribution 10-60 μm, composition (% by weight): Al 8.45, Mg 2.14, Fe 2.34, Si 32.8, Na 2.62 The main metal atom = Al) was dispersed in 240 g, heated to 101 ° C. over 1 hour, maintained at that temperature for 2 hours, and then cooled to 50 ° C. over 1 hour. The ionic strength was 8.55 ml / L. This slurry was filtered under reduced pressure to recover the cake. Furthermore, this cake was washed with distilled water until the pH of the final washing solution exceeded 3.5, and dried overnight at 110 ° C. under a nitrogen atmosphere to obtain 201.2 g of chemically treated montmorillonite.
This was sieved with a sieve having an opening of 75 μm to obtain particles having an average particle diameter of 24.7 μm.
As a result of the composition analysis, the elution rate of Al was 22%. The average pore diameter measured by the nitrogen adsorption method was 4.8 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.33 ml / g. The BET specific surface area was 275 m 2 / g.
２．触媒の調製およびプロピレンとエチレンの重合
前記化学処理したモンモリロナイトを減圧下、２００℃で、２時間乾燥を実施した。内容積１リットルの攪拌翼のついたガラス製反応器に、上記で得た乾燥モンモリロナイト２０ｇを導入し、トルエンを３％含むヘプタン（以下、混合ヘプタンと略称する）、さらにトリエチルアルミニウムのヘプタン溶液（０．５９６Ｍ）８４ｍｌを加え、室温で攪拌した。１時間後、混合ヘプタンにて洗浄（残液率１％未満）し、珪酸塩スラリーを２００ｍｌに調製した。
次に、予め（ｒ）−ジメチルシリレンビス｛１−［２―メチル−４−（４−クロロフェニル）−４Ｈ−アズレニル］｝ジルコニウムジクロリドを２１８ｍｇ（０．３ｍｍｏｌ）に混合ヘプタンを８７ｍｌ添加し、充分撹拌した後に、トリイソブチルアルミニウムのヘプタン溶液（０．７０６Ｍ）を４．２５ｍｌ加え、室温にて１時間反応させた。
その後、先に調製した珪酸塩スラリーに加え、１時間攪拌後、混合ヘプタンを追加して５００ｍｌに調製した。続いて、窒素で十分置換を行った内容積１．０リットルの攪拌式オートクレーブに、先に調製した珪酸塩／メタロセン錯体スラリーを導入した。温度が４０℃に安定したところでプロピレンを１０ｇ／時間の速度で供給し、温度を維持した。４時間後、プロピレンの供給を停止し、５０℃に昇温後、さらに２時間維持した。サイホンにて予備重合触媒スラリーを回収し、上澄みを約３００ｍｌ除き、４５℃にて減圧下乾燥した。
その結果、触媒１ｇ当たりポリプロピレン０．４９ｇを含む予備重合触媒を３０．１ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、１１０００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは２．４５ｇ／１０分、ポリマーの嵩密度は０．３１ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene and ethylene The chemically treated montmorillonite was dried at 200 ° C. under reduced pressure for 2 hours. 20 g of the dried montmorillonite obtained above was introduced into a glass reactor equipped with a stirring blade having an internal volume of 1 liter, heptane containing 3% toluene (hereinafter abbreviated as mixed heptane), and a heptane solution of triethylaluminum ( 0.596M) was added and stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane (residual liquid ratio less than 1%) to prepare a silicate slurry to 200 ml.
Next, (r) -dimethylsilylenebis {1- [2-methyl-4- (4-chlorophenyl) -4H-azurenyl]} zirconium dichloride was added to 218 mg (0.3 mmol) and 87 ml of heptane was added. After stirring, 4.25 ml of a heptane solution of triisobutylaluminum (0.706 M) was added and reacted at room temperature for 1 hour.
Then, in addition to the previously prepared silicate slurry, after stirring for 1 hour, mixed heptane was added to prepare 500 ml. Subsequently, the previously prepared silicate / metallocene complex slurry was introduced into a stirring autoclave having an internal volume of 1.0 liter sufficiently substituted with nitrogen. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped, the temperature was raised to 50 ° C., and then maintained for another 2 hours. The prepolymerized catalyst slurry was recovered with a siphon, and about 300 ml of the supernatant was removed, followed by drying at 45 ° C. under reduced pressure.
As a result, 30.1 g of a prepolymerized catalyst containing 0.49 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalyst activity was 11000 g-PP / g-catalyst, MFR was 2.45 g / 10 min, and the bulk density of the polymer was 0.31 g / cm 3 . The results are shown in Table 1.
［比較例１１］
１．イオン交換性層状珪酸塩の化学処理
処理（維持）時間を８時間とする以外は、比較例１０と同様に実施した。１８５．４ｇの化学処理モンモリロナイトを得た。
これを目開き７５μｍの篩にて篩い分けし、平均粒径が２４．８μｍの粒子を得た。
組成分析の結果、Ａｌの溶出率は３１％であった。窒素吸着法により測定した平均細孔径は５．２ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１３ｍｌ／ｇであった。ＢＥＴ比表面積は３２６ｍ２／ｇであった。
[Comparative Example 11]
1. Chemical treatment of ion-exchange layered silicate The same procedure as in Comparative Example 10 was conducted except that the treatment (maintenance) time was 8 hours. 185.4 g of chemically treated montmorillonite was obtained.
This was sieved with a sieve having an opening of 75 μm to obtain particles having an average particle diameter of 24.8 μm.
As a result of the composition analysis, the elution rate of Al was 31%. The average pore diameter measured by the nitrogen adsorption method was 5.2 nm, and the micropore volume within the pore diameter range of 2 to 6 nm was 0.13 ml / g. The BET specific surface area was 326 m 2 / g.
２．触媒の調製およびプロピレンとエチレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、比較例１０に記載の方法と同様に、触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン０．７６ｇを含む予備重合触媒を３５．５ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレン重合を行った。その結果、触媒活性は、１００００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは０．５２ｇ／１０分、ポリマーの嵩密度は０．３５ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene and ethylene A catalyst was prepared in the same manner as in the method described in Comparative Example 10 except that the chemically treated montmorillonite described above was used.
As a result, 35.5 g of a prepolymerized catalyst containing 0.76 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalytic activity was 10000 g-PP / g-catalyst, the MFR was 0.52 g / 10 min, and the bulk density of the polymer was 0.35 g / cm 3 . The results are shown in Table 1.
［比較例１２］
１．イオン交換性層状珪酸塩の化学処理
撹拌翼と還流装置を取り付けた５００ｍＬの丸形三口フラスコに、蒸留水１８０ｇを投入し、９８％硫酸２０ｇを滴下し、内部温度を９０℃にした。そこへ、モンモリロナイト３０ｇ添加後撹拌した。イオン強度は３．３３ｍｏｌ／Ｌであった。
その後、９０℃で１時間反応させた。このスラリーを１５０ｍＬの蒸留水に注いで反応を停止し、ヌッチェと吸引瓶にアスピレータを接続した装置にて濾過した。得られたケーキを５００ｍＬの蒸留水に分散させ撹拌後濾過した。この操作を５回繰りかえした。回収したケーキを１２０℃で終夜乾燥した。
その結果、２２ｇの化学処理体を得た。これを目開き７５μｍの篩にて篩い分けし、平均粒径が２４．８μｍの粒子を得た。
組成分析の結果、Ａｌの溶出率は５％であった。窒素吸着法により測定した平均細孔径は６．３ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．０８ｍｌ／ｇであった。ＢＥＴ比表面積は１２３ｍ２／ｇであった。
この酸処理モンモリロナイトを容積２００ｍＬのフラスコに入れ、２００℃で減圧乾燥させガスの発生が収まってから、さらに２時間減圧乾燥した。
[Comparative Example 12]
1. Chemical treatment of ion-exchange layered silicate Into a 500 mL round three-necked flask equipped with a stirring blade and a reflux apparatus, 180 g of distilled water was added, 20 g of 98% sulfuric acid was added dropwise, and the internal temperature was set to 90 ° C. There, 30 g of montmorillonite was added and stirred. The ionic strength was 3.33 mol / L.
Then, it was made to react at 90 degreeC for 1 hour. The slurry was poured into 150 mL of distilled water to stop the reaction, and the slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle. The obtained cake was dispersed in 500 mL of distilled water, stirred and filtered. This operation was repeated 5 times. The collected cake was dried at 120 ° C. overnight.
As a result, 22 g of a chemically treated product was obtained. This was sieved with a sieve having an opening of 75 μm to obtain particles having an average particle diameter of 24.8 μm.
As a result of the composition analysis, the elution rate of Al was 5%. The average pore diameter measured by the nitrogen adsorption method was 6.3 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.08 ml / g. The BET specific surface area was 123 m2 / g.
This acid-treated montmorillonite was placed in a 200 mL volumetric flask and dried under reduced pressure at 200 ° C., and after the generation of gas had ceased, it was further dried under reduced pressure for 2 hours.
２．触媒の調製およびプロピレンとエチレンの重合
内容積２００ｍＬのフラスコに上記乾燥した化学処理モンモリロナイト３ｇを秤量し、ヘプタン１０ｍＬ、トリエチルアルミニウムのヘプタン溶液２０ｍＬ（７．５ｍｍｏｌ）を加え、室温で１時間撹拌した。その後、トルエンで残液率１／１００まで洗浄し、最後にスラリー量を５ｍｌにあわせた。
次に、予め（ｒ）−ジメチルシリレンビス｛１−［２―メチル−４−（４−クロロフェニル）−４Ｈ−アズレニル］｝ジルコニウムジクロリドを３３ｍｇ（０．０４ｍｍｏｌ）に混合ヘプタンを１３ｍｌ添加し、充分撹拌した後に、トリイソブチルアルミニウムのヘプタン溶液（０．７０６Ｍ）を６．３ｍｌ加え、室温にて１時間反応させておき，前記の有機アルミニウム化合物処理モンモリロナイトのヘプタンスラリー（５ｍｌ）に全量添加した。室温で１時間撹拌した後、室温、減圧下で溶媒を留去することにより、担持触媒を得た。重合を行う前に、担持触媒をヘプタンで希釈（１０ｍｇ固体触媒／ｍｌヘプタン）し、重合評価に用いた。重合は、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。
その結果、触媒活性は、５０００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは３．２ｇ／１０分、ポリマーの嵩密度は０．４０ｇ／ｃｍ３であった。結果を表１に示す。
2. Preparation of catalyst and polymerization of propylene and ethylene 3 g of the dried chemically treated montmorillonite was weighed into a flask with an internal volume of 200 mL, 10 mL of heptane and 20 mL (7.5 mmol) of a heptane solution of triethylaluminum were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the residue was washed with toluene to a residual liquid ratio of 1/100, and finally the amount of slurry was adjusted to 5 ml.
Next, 13 ml of heptane mixed with 33 mg (0.04 mmol) of (r) -dimethylsilylenebis {1- [2-methyl-4- (4-chlorophenyl) -4H-azurenyl]} zirconium dichloride was added in advance. After stirring, 6.3 ml of a heptane solution of triisobutylaluminum (0.706 M) was added and allowed to react at room temperature for 1 hour, and the whole amount was added to the heptane slurry (5 ml) of the above-described organoaluminum compound-treated montmorillonite. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure at room temperature to obtain a supported catalyst. Before the polymerization, the supported catalyst was diluted with heptane (10 mg solid catalyst / ml heptane) and used for the polymerization evaluation. Polymerization was carried out in the same manner as described in Example 4 to polymerize propylene and ethylene.
As a result, the catalytic activity was 5000 g-PP / g-catalyst, the MFR was 3.2 g / 10 min, and the bulk density of the polymer was 0.40 g / cm 3 . The results are shown in Table 1.
［比較例１３］
１．イオン交換性層状珪酸塩の化学処理
セパラブルフラスコ中で８．２ｗｔ％硫酸マグネシウム水溶液（７９３ｇ）に、水澤化学社製ベンクレイＳＬ（スメクタイト：１００ｇ，Ａｌ／Ｓｉ＝０．２８３、主金属原子＝Ａｌ）を３０℃で加えてスラリー化した。このスラリーを０．６℃／分で２時間かけて１００℃まで昇温し、１００℃で６０分反応させた。このときのイオン強度は３．７９ｍｏｌ／Ｌであった。
その後１００℃のままその反応スラリーに９６％硫酸（１０９ｇ）を１２分かけて滴下、さらに１０８分間１００℃で反応させた。このときのイオン強度は８．１６ｍｏｌ／Ｌであった。
この反応スラリーを１時間で室温まで冷却し、蒸留水でｐＨ３まで洗浄した。得られた固体を窒素気流下１３０℃で２日間予備乾燥後、さらに２００℃で２時間減圧乾燥することにより、化学処理スメクタイト２２．９ｇを得た。
この化学処理スメクタイトの組成は、Ａｌ：７．６ｗｔ％、Ｓｉ：３４．５ｗｔ％、Ｍｇ１．９ｗｔ％、Ｆｅ：２．２ｗｔ％、Ｎａ＜０．２ｗｔ％であり、Ａｌ／Ｓｉ＝０．２２９［ｍｏｌ／ｍｏｌ］，Ａｌの溶出量は１９％であった。また、平窒素吸着法により測定した平均細孔径は６．１ｎｍ，２−６ｎｍの範囲の微小細孔量は０．１４ｍＬ／ｇ，表面積は２６８ｍ２／ｇであった。
[Comparative Example 13]
1. Chemical treatment of ion-exchange layered silicate In a separable flask, 8.2 wt% magnesium sulfate aqueous solution (793 g) was added to Benclay SL (Smectite: 100 g, Al / Si = 0.283, main metal atom = Al ) At 30 ° C. to make a slurry. The slurry was heated to 100 ° C. over 2 hours at 0.6 ° C./minute, and reacted at 100 ° C. for 60 minutes. The ionic strength at this time was 3.79 mol / L.
Thereafter, 96% sulfuric acid (109 g) was added dropwise over 12 minutes to the reaction slurry while maintaining the temperature at 100 ° C., and the reaction was further performed at 100 ° C. for 108 minutes. The ionic strength at this time was 8.16 mol / L.
The reaction slurry was cooled to room temperature in 1 hour and washed to pH 3 with distilled water. The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and further dried under reduced pressure at 200 ° C. for 2 hours to obtain 22.9 g of chemically treated smectite.
The composition of this chemically treated smectite is Al: 7.6 wt%, Si: 34.5 wt%, Mg 1.9 wt%, Fe: 2.2 wt%, Na <0.2 wt%, and Al / Si = 0.229. [Mol / mol], the elution amount of Al was 19%. Moreover, the average pore diameter measured by the flat nitrogen adsorption method was 6.1 nm, the amount of micropores in the range of 2-6 nm was 0.14 mL / g, and the surface area was 268 m 2 / g.
２．予備重合（以下の操作は、すべて乾燥窒素雰囲気下で行った。）
上で得られた化学処理スメクタイト２０ｇをヘプタン（１８３ｍＬ）スラリーとし、これにトリエチルアルミニウム（１０ｍｍｏｌ：濃度６８ｍｇ／ｍＬのヘプタン溶液を１６．８ｍＬ）を加えて１時間攪拌後、ヘプタンで１／１００まで洗浄した。このスラリーを１Ｌオートクレーブに導入した。
また、別途ジメチルシリレンビス（２−メチル−４−（ｐ−クロロフェニル）ジヒドロアズレニル）ジルコニウムジクロリド（０．３ｍｍｏｌ）のトルエン８７ｍＬ溶液にトリイソブチルアルミニウム（３ｍｍｏｌ：濃度１４０ｍｇ／ｍＬのヘプタン溶液を４．２６ｍＬ）を加えて反応させた溶液を、上記オートクレーブに加えた。さらに、ヘプタンを２１０ｍＬ追加したのち４０℃でプロピレンを２０ｇ／ｈの速度で２時間フィードし、予備重合を行った。その後、プロピレンフィードを止めて、さらに２時間４０℃で残重合を行った。得られた触媒スラリーの上澄みを除去した後、失活防止剤としてトリイソブチルアルミニウム（１２ｍｍｏｌ：濃度１４０ｍｇ／ｍＬのヘプタン溶液を１７ｍＬ）を加えて１０分攪拌した。この固体を３時間減圧乾燥することにより、触媒１ｇ当たりポリプロピレン１．５０ｇを含む乾燥予備重合触媒を５０．２ｇ得た。
2. Prepolymerization (All the following operations were performed under a dry nitrogen atmosphere.)
20 g of the chemically treated smectite obtained above was made into a heptane (183 mL) slurry, triethylaluminum (10 mmol: 16.8 mL of 68 mg / mL concentration of heptane solution) was added thereto, and the mixture was stirred for 1 hour, and then reduced to 1/100 with heptane. Washed. This slurry was introduced into a 1 L autoclave.
Separately, a solution of dimethylsilylene bis (2-methyl-4- (p-chlorophenyl) dihydroazurenyl) zirconium dichloride (0.3 mmol) in 87 mL of toluene was added to a solution of triisobutylaluminum (3 mmol: 140 mg / mL in heptane). 26 mL) was added and reacted, and the solution was added to the autoclave. Further, 210 mL of heptane was added, and propylene was fed at a rate of 20 g / h for 2 hours at 40 ° C. to perform prepolymerization. Thereafter, the propylene feed was stopped, and the remaining polymerization was further performed at 40 ° C. for 2 hours. After removing the supernatant of the obtained catalyst slurry, triisobutylaluminum (12 mmol: 17 mL of a heptane solution having a concentration of 140 mg / mL) was added as a deactivation inhibitor and stirred for 10 minutes. This solid was dried under reduced pressure for 3 hours to obtain 50.2 g of a dry prepolymerized catalyst containing 1.50 g of polypropylene per 1 g of the catalyst.
３．プロピレンとエチレンの重合
このようにして得た触媒を用いて，実施例４記載と同様にして、プロピレンとエチレンの重合を行った。
その結果、触媒活性は、１２０００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．１ｇ／１０分、ポリマーの嵩密度は０．４０ｇ／ｃｍ３であった。結果を表１に示す。
3. Polymerization of propylene and ethylene Polymerization of propylene and ethylene was carried out in the same manner as described in Example 4 using the catalyst thus obtained.
As a result, the catalyst activity was 12000 g-PP / g-catalyst, MFR was 1.1 g / 10 min, and the bulk density of the polymer was 0.40 g / cm 3 . The results are shown in Table 1.
［比較例１４］
１．イオン交換性層状珪酸塩の化学処理
セパラブルフラスコ中で８．２ｗｔ％硫酸マグネシウム水溶液（７９３ｇ）に９６％硫酸（２７ｇ）を加え、さらに水沢化学社製ベンクレイＳＬ（１００ｇ）を３０℃で加えてスラリー化した。このときイオン強度は４．８８ｍｏｌ／Ｌであった。
このスラリーを０．６℃／分で２時間かけて１００℃まで昇温し１００℃で６０分反応させた。その後１００℃のままその反応スラリーに９６％硫酸（１９１ｇ）を２６分かけて滴下し、さらに９４分間１００℃で反応させた。このときイオン強度は１２．４９ｍｏｌ／Ｌであった。
この反応スラリーを１時間で室温まで冷却し、蒸留水でｐＨ３まで洗浄した。得られた固体を窒素気流下１３０℃で２日間予備乾燥後、さらに２００℃で２時間減圧乾燥することにより化学処理スメクタイト３３．０ｇを得た。
この化学処理スメクタイトの組成は、Ａｌ：６．５ｗｔ％、Ｓｉ：３５．３ｗｔ％、であり、Ａｌ／Ｓｉ＝０．１９２［ｍｏｌ／ｍｏｌ］で、Ａｌの溶出率は３２％であった。窒素吸着法により測定した平均細孔径は５．７ｎｍ、細孔径２〜６ｎｍの範囲の微小細孔容積は０．１１ｍｌ／ｇであった。ＢＥＴ比表面積は２７７ｍ２／ｇであった。
[Comparative Example 14]
1. Chemical treatment of ion-exchange layered silicate In a separable flask, 96% sulfuric acid (27 g) was added to 8.2 wt% magnesium sulfate aqueous solution (793 g), and Benclay SL (100 g) manufactured by Mizusawa Chemical Co., Ltd. was added at 30 ° C. Slurried. At this time, the ionic strength was 4.88 mol / L.
This slurry was heated to 100 ° C. over 2 hours at 0.6 ° C./min and reacted at 100 ° C. for 60 minutes. Thereafter, 96% sulfuric acid (191 g) was added dropwise over 26 minutes to the reaction slurry while maintaining the temperature at 100 ° C., and the mixture was further reacted at 100 ° C. for 94 minutes. At this time, the ionic strength was 12.49 mol / L.
The reaction slurry was cooled to room temperature in 1 hour and washed to pH 3 with distilled water. The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and further dried under reduced pressure at 200 ° C. for 2 hours to obtain 33.0 g of chemically treated smectite.
The composition of this chemically treated smectite was Al: 6.5 wt%, Si: 35.3 wt%, Al / Si = 0.192 [mol / mol], and the elution rate of Al was 32%. The average pore diameter measured by the nitrogen adsorption method was 5.7 nm, and the micropore volume in the pore diameter range of 2 to 6 nm was 0.11 ml / g. The BET specific surface area was 277 m 2 / g.
２．触媒の調製およびプロピレンとエチレンの重合
上記記載の化学処理モンモリロナイトを使用する以外は、比較例１１に記載の方法と同様に触媒の調製を行った。
その結果、触媒１ｇ当たりポリプロピレン０．６６ｇを含む予備重合触媒を３３．２ｇ得た。これを用いて、実施例４記載と同様にして、プロピレンとエチレンの重合を行った。その結果、触媒活性は、１００００ｇ−ＰＰ／ｇ−触媒、ＭＦＲは１．６ｇ／１０分、ポリマーの嵩密度は０．４２ｇ／ｃｍ３であった。結果を表１に示す。
尚、表１中、微小細孔は、細孔径２〜６ｎｍの微小細孔容積であり、細孔容積は、メソ細孔容積である。
2. Catalyst Preparation and Polymerization of Propylene and Ethylene A catalyst was prepared in the same manner as described in Comparative Example 11 except that the chemically treated montmorillonite described above was used.
As a result, 33.2 g of a prepolymerized catalyst containing 0.66 g of polypropylene per 1 g of catalyst was obtained. Using this, propylene and ethylene were polymerized in the same manner as described in Example 4. As a result, the catalytic activity was 10,000 g-PP / g-catalyst, the MFR was 1.6 g / 10 min, and the bulk density of the polymer was 0.42 g / cm 3 . The results are shown in Table 1.
In Table 1, the micropore is a micropore volume having a pore diameter of 2 to 6 nm, and the pore volume is a mesopore volume.
表１から、プロピレンの単独重合で評価した実施例１〜３の触媒は、イオン交換性層状珪酸塩の平均細孔径が２〜６ｎｍであり、かつ微小細孔容量が０．１４ｍｌ／ｇ以上と大きいため、同じ条件で評価した比較例１〜５の触媒に比べて，触媒活性が高いことがわかる。また、エチレンとプロピレンの共重合で評価した実施例４〜１１の触媒も、同様に、同じ条件で評価した比較例６〜１４の触媒に比べて、触媒活性が高いことがわかる。 From Table 1, the catalysts of Examples 1 to 3 evaluated by homopolymerization of propylene have an ion-exchange layered silicate average pore diameter of 2 to 6 nm and a micropore volume of 0.14 ml / g or more. Since it is large, it turns out that catalyst activity is high compared with the catalyst of Comparative Examples 1-5 evaluated on the same conditions. Moreover, it turns out that the catalyst of Examples 4-11 evaluated by copolymerization of ethylene and propylene also has a higher catalytic activity than the catalysts of Comparative Examples 6-14 evaluated under the same conditions.
本発明の特定のイオン交換性層状珪酸塩からなるオレフィン重合用触媒成分、およびそれを用いたオレフィン重合用触媒は、重合が高活性に進行し、得られるポリマーパウダーのかさ密度が高く、良好な性状のポリオレフィンの製造が可能となり、産業上、利用可能性が高い。 The olefin polymerization catalyst component comprising the specific ion-exchange layered silicate of the present invention, and the olefin polymerization catalyst using the same, the polymerization proceeds with high activity, and the bulk density of the resulting polymer powder is high and good. This makes it possible to produce polyolefin with properties, and is highly applicable in industry.
Claims (7)
特性１：イオン交換性層状珪酸塩の窒素吸着法により測定した平均細孔径が２〜６ｎｍであること。
特性２：イオン交換性層状珪酸塩の窒素吸着法により測定した細孔径２〜６ｎｍの範囲の微小細孔容積が０．１４ｍｌ／ｇ以上であること。 A catalyst component for olefin polymerization, comprising an ion-exchange layered silicate that satisfies the following characteristics 1 and 2.
Characteristic 1: The average pore diameter measured by the nitrogen adsorption method of the ion-exchange layered silicate is 2 to 6 nm.
Characteristic 2: The micropore volume in the range of pore diameter of 2 to 6 nm measured by the nitrogen adsorption method of ion-exchange layered silicate is 0.14 ml / g or more.
イオン強度（ｍｏｌ／Ｌ）＝０．５×Σ（溶液中のイオンのモル濃度ｍｏｌ／Ｌ×（イオンの電荷数）２）・・・数式（１） 2. The olefin polymerization catalyst according to claim 1, wherein the catalyst is chemically treated under the condition that the ionic strength in the solution defined by the following formula (1) is 0.05 to 8.00 mol / L. component.
Ionic strength (mol / L) = 0.5 × Σ (mol concentration of ions in solution mol / L × (number of charges of ions) 2 ) (1)
成分（ａ）：周期率表４〜６族遷移金属のメタロセン化合物
成分（ｂ）：請求項１〜５のいずれかに記載のイオン交換性層状珪酸塩
成分（ｃ）：有機アルミニウム化合物 A catalyst for olefin polymerization comprising the following component (a), component (b) and, if necessary, component (c).
Component (a): Metallocene compound of Periodic Table 4 to 6 transition metal Component (b): Ion exchange layered silicate according to any of claims 1 to 5 Component (c): Organoaluminum compound
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012070510A JP5870802B2 (en) | 2011-03-30 | 2012-03-27 | Olefin polymerization catalyst component, olefin polymerization catalyst and polyolefin production method using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011074969 | 2011-03-30 | ||
| JP2011074969 | 2011-03-30 | ||
| JP2012070510A JP5870802B2 (en) | 2011-03-30 | 2012-03-27 | Olefin polymerization catalyst component, olefin polymerization catalyst and polyolefin production method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012214745A true JP2012214745A (en) | 2012-11-08 |
| JP5870802B2 JP5870802B2 (en) | 2016-03-01 |
Family
ID=47267825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012070510A Active JP5870802B2 (en) | 2011-03-30 | 2012-03-27 | Olefin polymerization catalyst component, olefin polymerization catalyst and polyolefin production method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5870802B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015060421A1 (en) | 2013-10-25 | 2015-04-30 | 日本ポリプロ株式会社 | Catalyst component for olefin polymerization, and catalyst for olefin polymerization and process for producing olefin (co)polymer using same |
| JP2016199735A (en) * | 2015-04-07 | 2016-12-01 | 日本ポリプロ株式会社 | Solid acid, olefin polymerization catalyst, and production method of olefin polymer |
| JP2019172958A (en) * | 2018-03-26 | 2019-10-10 | 日本ポリプロ株式会社 | Manufacturing method of catalyst component for olefin polymerization, manufacturing method of catalyst for olefin polymerization, and manufacturing method of olefin polymer using the same |
| WO2020203274A1 (en) | 2019-03-29 | 2020-10-08 | 日本ポリプロ株式会社 | Production method for catalyst component for olefin polymerization, production method for catalyst for olefin polymerization, and production method for olefin polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09286814A (en) * | 1996-02-23 | 1997-11-04 | Tosoh Corp | Olefin polymerization catalyst using organometallic complex and production of polyolefin using the same |
| JP2006312748A (en) * | 2001-04-09 | 2006-11-16 | Japan Polypropylene Corp | Catalyst for olefin polymerization and method of polyolefin production |
| JP2007106846A (en) * | 2005-10-12 | 2007-04-26 | Japan Polypropylene Corp | Catalyst carrier for olefin polymerization, and catalyst component for olefin polymerization by using the same |
| JP2007517960A (en) * | 2004-01-07 | 2007-07-05 | エクソンモービル・ケミカル・パテンツ・インク | Supported activator |
-
2012
- 2012-03-27 JP JP2012070510A patent/JP5870802B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09286814A (en) * | 1996-02-23 | 1997-11-04 | Tosoh Corp | Olefin polymerization catalyst using organometallic complex and production of polyolefin using the same |
| JP2006312748A (en) * | 2001-04-09 | 2006-11-16 | Japan Polypropylene Corp | Catalyst for olefin polymerization and method of polyolefin production |
| JP2007517960A (en) * | 2004-01-07 | 2007-07-05 | エクソンモービル・ケミカル・パテンツ・インク | Supported activator |
| JP2007106846A (en) * | 2005-10-12 | 2007-04-26 | Japan Polypropylene Corp | Catalyst carrier for olefin polymerization, and catalyst component for olefin polymerization by using the same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015060421A1 (en) | 2013-10-25 | 2015-04-30 | 日本ポリプロ株式会社 | Catalyst component for olefin polymerization, and catalyst for olefin polymerization and process for producing olefin (co)polymer using same |
| JP2015108138A (en) * | 2013-10-25 | 2015-06-11 | 日本ポリプロ株式会社 | Catalyst component for olefin polymerization, olefin polymerization catalyst, and method for producing olefin (co)polymer using the catalyst |
| US9751961B2 (en) | 2013-10-25 | 2017-09-05 | Japan Polypropylene Corporation | Catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing olefin (co)polymer using the same |
| JP2018111841A (en) * | 2013-10-25 | 2018-07-19 | 日本ポリプロ株式会社 | Catalyst component for olefin polymerization, catalyst for olefin polymerization and manufacturing method of olefin (co)polymer using the same |
| JP2016199735A (en) * | 2015-04-07 | 2016-12-01 | 日本ポリプロ株式会社 | Solid acid, olefin polymerization catalyst, and production method of olefin polymer |
| JP2019172958A (en) * | 2018-03-26 | 2019-10-10 | 日本ポリプロ株式会社 | Manufacturing method of catalyst component for olefin polymerization, manufacturing method of catalyst for olefin polymerization, and manufacturing method of olefin polymer using the same |
| JP7092002B2 (en) | 2018-03-26 | 2022-06-28 | 日本ポリプロ株式会社 | A method for producing a catalyst component for olefin polymerization, a method for producing a catalyst for olefin polymerization, and a method for producing an olefin polymer using the same. |
| WO2020203274A1 (en) | 2019-03-29 | 2020-10-08 | 日本ポリプロ株式会社 | Production method for catalyst component for olefin polymerization, production method for catalyst for olefin polymerization, and production method for olefin polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5870802B2 (en) | 2016-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2018111841A (en) | Catalyst component for olefin polymerization, catalyst for olefin polymerization and manufacturing method of olefin (co)polymer using the same | |
| JP5870802B2 (en) | Olefin polymerization catalyst component, olefin polymerization catalyst and polyolefin production method using the same | |
| JP4244403B2 (en) | Catalyst component or catalyst for propylene polymerization | |
| WO2003002616A1 (en) | Catalyst for olefin polymerization and method for polymerization of olefin | |
| JP5794189B2 (en) | Olefin polymerization catalyst component and process for producing the same, olefin polymerization catalyst and process for producing polyolefin using the same | |
| JP2002037812A (en) | Olefin polymerization catalyst and method for producing polyolefin using the same | |
| JP5520865B2 (en) | Method for producing layered silicate particles and method for producing olefin polymerization catalyst using the same | |
| JP7092002B2 (en) | A method for producing a catalyst component for olefin polymerization, a method for producing a catalyst for olefin polymerization, and a method for producing an olefin polymer using the same. | |
| JP6136852B2 (en) | Olefin polymerization catalyst component, catalyst component production method, olefin polymerization catalyst and olefin (co) polymer production method using the same | |
| JPH111508A (en) | Catalytic component for alpha-olefin polymerization, catalyst and production of alpha-olefin polymer | |
| JPH11166011A (en) | Catalyst component for alpha-olefin polymerization, catalyst, and production of alpha-olefin polymer | |
| JP4106221B2 (en) | Method for producing catalyst component for olefin polymerization | |
| JP2002053609A (en) | Catalyst for olefin polymerization | |
| JP2004051715A (en) | Olefin polymerization catalyst and process for producing polyolefin | |
| JP5508660B2 (en) | Ion exchange layered silicate particles and production method thereof, olefin polymerization catalyst comprising the same, and production method of olefin polymer using the same | |
| JP4820472B2 (en) | Olefin polymerization catalyst component, olefin polymerization catalyst and polyolefin production method using the same | |
| JP6187350B2 (en) | Method for producing layered silicate, method for producing catalyst component for olefin polymerization, and method for producing catalyst for olefin polymerization | |
| JP4794246B2 (en) | Method for producing catalyst carrier for olefin polymerization, catalyst component for olefin polymerization using the same | |
| JP4966482B2 (en) | Process for producing ion-exchangeable layered silicate particles, catalyst component for olefin polymerization using the same | |
| JP2012126084A (en) | Clay mineral particle and method of producing the same, and olefin polymerization catalyst using the same | |
| JP6838420B2 (en) | A method for producing a catalyst component for olefin polymerization, a method for producing a catalyst for olefin polymerization, and a method for producing an olefin polymer. | |
| JP2000080117A (en) | Preparation of olefin polymerization catalyst component | |
| JP2002284808A (en) | Olefin polymerization catalyst and production method for polyolefin | |
| JP2003020304A (en) | Catalyst component for olefin polymerization, catalyst for olefin polymerization, and method of manufacturing catalyst component for olefin polymerization | |
| WO2022059764A1 (en) | Ion-exchangeable layered silicate salt particles, olefin polymerization catalyst component, olefin polymerization catalyst, method for producing olefin polymerization catalyst, and method for producing olefin polymer using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140630 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20141127 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20141209 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150203 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150512 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20150529 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150629 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20150629 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150929 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151105 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20151215 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20151228 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5870802 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |